CN101492375B - Synthesis of 4-tert-butyl cyclohexyl chloride formic ester - Google Patents

Synthesis of 4-tert-butyl cyclohexyl chloride formic ester Download PDF

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CN101492375B
CN101492375B CN2009100214565A CN200910021456A CN101492375B CN 101492375 B CN101492375 B CN 101492375B CN 2009100214565 A CN2009100214565 A CN 2009100214565A CN 200910021456 A CN200910021456 A CN 200910021456A CN 101492375 B CN101492375 B CN 101492375B
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tert
cyclohexyl chloride
formic ester
butyl cyclohexyl
butyl
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CN101492375A (en
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张有明
赵堃
魏太保
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Northwest Normal University
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Abstract

The invention relates to a chemical synthesis method of 4-tert-butyl cyclohexyl chloride formate. In the method, 4- tert-butyl cyclohexanol and double(trichloromethyl) carbonic acid ester are taken as the raw materials and react for 6 to 30h at 15 to 60 DEG C in the organic solvent under the action of an inorganic catalyst; after the reaction, the catalyst is removed and separated, the solvent is distilled out of the mother liquid, then a column separation method is adopted for separation and the separated product is recrystallized in petroleum ether for 5 to 24h at -5 to 10 DEG C; finally the white crystal is the target product. In the invention, the solid inorganic catalyst is adopted to replace the traditional organic amine catalyst, thus facilitating the catalyst recovery and greatly reducing the environmental pollution. Meanwhile, the catalyst can be directly put into use without treatment, thus reducing the synthesis cost. The 4-tert-butyl cyclohexyl chloride formate synthesized by the invention is good in quality, the purity is more than or equal to 98 percent and the yield is high, generally 75 to 90 percent.

Description

The compound method of 4-tert-butyl cyclohexyl chloride formic ester
Technical field
The invention belongs to chemosynthesis technical field, relate to a kind of chemical synthesis process of 4-tert-butyl cyclohexyl chloride formic ester, relate in particular to a kind of method of under the effect of organic catalyst, synthesizing the 4-tert-butyl cyclohexyl chloride formic ester.
Background technology
The chloroformic acid lipoid substance is a kind of broad-spectrum chemical intermediate, can be used for medicine intermediate, pesticide intermediate, also can be used as the raw material of synthetic initiator.The 4-tert-butyl cyclohexyl chloride formic ester has very big practical value as the chemical reagent midbody, has very big economic worth as the raw material of initiator.
At present, the compound method of chloroformic acid fat mainly adopts two kinds of methods: be raw material with fatty alcohols and phenols 1,, under the phosgene condition, react and make.This is reflected at has detailed introduction among the CN200580043526.2, fatty alcohols and phenols are raw material, under the condition of two (trichloromethyl) carbonic ether, react, and this is reflected at Cotarca, L; Delogu, P; Nardelli, A.Synthesis 1996, and detailed introduction is arranged among the 553-576.But phosgene is a kind of and dangerous hypertoxicity gas, for metering accurately, causes potential safety hazard in the Chemical Manufacture kind, also must set up a corresponding phosgene production device simultaneously, has increased production cost virtually again.And the reaction of two (trichloromethyl) carbonic ether, major part all is that the organic cpds acid binding agent of amino-contained is the reaction of catalyzer, makes that catalyzer is difficult for reclaiming, and causes chemical pollution, and cost raises, and aftertreatment is complicated.
Summary of the invention
It is a kind of simple to operate that the object of the invention is to provide, and production safety is reliable, and cost is low, the method for the synthetic 4-tert-butyl cyclohexyl chloride formic ester that environmental pollution is little.
The method of the synthetic 4-tert-butyl cyclohexyl chloride formic ester of the present invention is to be raw material with 4-tertiary butyl hexalin with two (trichloromethyl) carbonic ethers, under the effect of organic catalyst, in organic solvent, in 15～60 ℃ of reaction 6～30h; After reaction finishes, filter to isolate catalyzer, and after mother liquor steamed solvent, adopt the post separate mode to separate, the product after the separation, obtains white crystal and is title product at-5～10 ℃ of following recrystallization 5～24h with sherwood oil.
Its reaction equation is following:
Figure G2009100214565D00021
Said 4-tertiary butyl hexalin is 1: 0.3～1: 0.9 with the mol ratio of two (trichloromethyl) carbonic ethers; Preferred 1: 0.3～1: 0.7; The best is 1: 0.7.
The mass ratio of said 4-tertiary butyl hexalin and organic catalyst is 1: 0.5～1: 2; The best was 1: 0.8 in preferred 1: 0.5～1: 1.
The organic catalyst that the present invention adopts comprises permutite, ZSM-5 molecular sieve, mordenite, beta-molecular sieve, Y zeolite, gac etc. for being main porous molecular screen with the silico-aluminate.Can select wherein any one during practical application for use.
The organic solvent that the present invention adopts is a Skellysolve A; Pentamethylene, normal hexane, hexanaphthene, sherwood oil, benzene, toluene, chlorobenzene, YLENE, methylene dichloride, trichloromethane, 1; 1-methylene dichloride, 1; 2-methylene dichloride, 1,1,1-trichloromethane, ETHYLE ACETATE, methyl acetate, propyl acetate; Butylacetate, isobutyl acetate, Isoamyl Acetate FCC, pentyl acetate, acetone, butanone, ketopentamethylene, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, THF, 1, any one in the 4-dioxane.The consumption of organic solvent is 10～30 times of 4-tertiary butyl hexalin volume.
Synthetic 4-tert-butyl cyclohexyl chloride formic ester of the present invention, through detecting, purity is >=98%, yield is 75～90%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
The present invention compared with prior art has the following advantages:
1, the present invention is raw material with 4-tertiary butyl hexalin with two (trichloromethyl) carbonic ethers, under the effect of organic catalyst, in organic solvent; In 15～60 ℃ of reaction 6～30h, after distillation removes and to desolvate, separate and get; Synthesis technique is simple, and synthesis condition is gentle, safety simple to operate; Synthetic cost is lower, and production has good practical value to large industrialized.
2, the present invention adopts the solid inorganic catalyzer to replace traditional organic amine catalyzer, and catalyst recovery is convenient, significantly reduces the pollution to environment.Simultaneously, catalyzer can directly continue to come into operation under not treated condition; And the repeated use of catalyzer has very big economic worth.
3, synthetic 4-tert-butyl cyclohexyl chloride formic ester of the present invention, quality better, purity is >=98%.
4, synthetic 4-tert-butyl cyclohexyl chloride formic ester of the present invention, yield is high, generally 75～90%.
Embodiment
Embodiment 1
In the round-bottomed flask of 250ml, add the methylene dichloride of 150ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 4.6881g (30mmol) and two (trichloromethyl) carbonic ether 6.2530g (21mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Add permutite 4g, at room temperature stirring reaction 24h.After reaction finishes, catalyst filtration is come out, and, steam solvent the mother liquor rotary distillation.(it is sherwood oil and methylene dichloride that post separates the solvent that adopts to cross the post separation after mother liquor being concentrated again; The volume ratio of sherwood oil and methylene dichloride is 2: 1); At last the product of separating is added an amount of sherwood oil, 24h carries out recrystallization in refrigerator-freezer, obtains the crystal of white.Filter, drying obtains the 4-tert-butyl cyclohexyl chloride formic ester crystal 5 .9g of white, and yield is 90%.Through detecting, purity is >=98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 2
In the round-bottomed flask of 250ml, add the methylene dichloride of 50ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 2.3440g (15mmol) and two (trichloromethyl) carbonic ether 3.1265g (10.5mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Add Y zeolite 2g.Other preparation condition and step all are same as embodiment 1, obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 2 .6g of white, and yield is 79%, and through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 3
In the round-bottomed flask of 250ml, add the methylene dichloride of 50ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 2.3440g (15mmol) and two (trichloromethyl) carbonic ether 3.1265g (10.5mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Add gac 2g.Other preparation process and condition all are same as embodiment 1, obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 2 .6g of white, and yield is 79%.Through detecting, purity is 99%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 4
In the round-bottomed flask of 250ml, add the methylene dichloride of 50ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 2.3440g (15mmol) and two (trichloromethyl) carbonic ether 3.1265g (10.5mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add the permutite 2g that reclaims once.Other preparation condition and step all are same as embodiment 1, obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 2 .82g of white, and yield is 86%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 5
In the round-bottomed flask of 250ml, add the methylene dichloride of 40ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 1.758g (11.25mmol) and two (trichloromethyl) carbonic ether 2.3449g (7.88mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add the permutite 1.5g that reclaims secondary, other preparation condition and step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 2 .14g of white, yield is 87%.Through detecting, purity is 99%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 6
In the round-bottomed flask of 250ml, add the methylene dichloride of 40ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 2.0315g (13mmol) and two (trichloromethyl) carbonic ether 2.7096g (9.10mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add the Y zeolite 1.7333g that reclaims once.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 2 .1326g of white, yield is 75%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 7
In the round-bottomed flask of 250ml, add the methylene dichloride of 40ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 1.5627g (10mmol) and two (trichloromethyl) carbonic ether 2.0843g (7.00mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add the Y zeolite 1.3333g that reclaims secondary.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 1.6452g of white, yield is 75%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 8
In the round-bottomed flask of 250ml, add the methylene dichloride of 50ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 2.0315g (13mmol) and two (trichloromethyl) carbonic ether 2.7096g (9.10mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add the gac 1.7333g that reclaims once.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 2 .1551g of white, yield is 76%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 9
In the round-bottomed flask of 250ml, add the methylene dichloride of 40ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 1.5627g (10mmol) and two (trichloromethyl) carbonic ether 2.0843g (7.00mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add the Y zeolite 1.3333g that reclaims secondary.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 1.8281g of white, yield is 83%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 10
In the round-bottomed flask of 250ml, add the methylene dichloride of 30ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 3.1254g (20mmol) and two (trichloromethyl) carbonic ether 2.9776g (10mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add permutite 2g.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 3 .075g of white, yield is 75%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 11
In the round-bottomed flask of 250ml, add the methylene dichloride of 30ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 3.1254g (20mmol) and two (trichloromethyl) carbonic ether 2.9776g (10mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add permutite 2.6g.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 3 .4213g of white, yield is 78%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 12
In the round-bottomed flask of 250ml, add the methylene dichloride of 30ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 3.1254g (20mmol) and two (trichloromethyl) carbonic ether 2.9776g (10mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add permutite 2.6g.At 40 ℃ of refluxed reaction 8h.Other preparation condition, step all are same as embodiment 1.Obtain the 4-tert-butyl cyclohexyl chloride formic ester crystal 3 .6675g of white, yield is 84%.Through detecting, purity is 98%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
Embodiment 13
In the round-bottomed flask of 250ml, add the sherwood oil of 60ml; Under magnetic stirring apparatus, 4-tertiary butyl hexalin 3.1254g (20mmol) and two (trichloromethyl) carbonic ether 4.1686g (14mmol) are joined in the round-bottomed flask, stirring is fully dissolved it; Then add permutite 2.0g, react 6h down at 50～60 ℃.Other treatment step all is same as embodiment 1, obtains the 4-tert-butyl cyclohexyl chloride formic ester crystal 3 .7582g of white, and yield is 86%.Through detecting, purity is 97%.Analyze through FTIR, at 1799cm -1, 1237cm -1, 1081cm -1There have the obvious characteristics peak to show to be consistent with title product.
The reaction conditions and the result of other catalyzer and solvent are similar to the above embodiments, repeat no more here.

Claims (6)

1. the compound method of a 4-tert-butyl cyclohexyl chloride formic ester is to be raw material with 4-tertiary butyl hexalin with two (trichloromethyl) carbonic ethers, under the effect of organic catalyst, in organic solvent, in 15～60 ℃ of reaction 6～30h; After reaction finishes, filter to isolate catalyzer, and after mother liquor steamed solvent, adopt the post separate mode to separate, the product after the separation, obtains white crystal and is title product at-5～10 ℃ of following recrystallization 5～24h with sherwood oil.
2. the compound method of 4-tert-butyl cyclohexyl chloride formic ester according to claim 1, it is characterized in that: said 4-tertiary butyl hexalin is 1: 0.3～1: 0.9 with the mol ratio of two (trichloromethyl) carbonic ethers.
3. the compound method of 4-tert-butyl cyclohexyl chloride formic ester according to claim 1, it is characterized in that: the mass ratio of said 4-tertiary butyl hexalin and catalyzer is 1: 0.5～1: 2.
4. the compound method of 4-tert-butyl cyclohexyl chloride formic ester according to claim 1, it is characterized in that: said organic catalyst is permutite, mordenite or gac.
5. the compound method of 4-tert-butyl cyclohexyl chloride formic ester according to claim 1; It is characterized in that: said organic solvent is a Skellysolve A; Pentamethylene, normal hexane, hexanaphthene, sherwood oil, benzene, toluene, chlorobenzene, YLENE, methylene dichloride, trichloromethane, ETHYLE ACETATE, methyl acetate, propyl acetate; Butylacetate, isobutyl acetate, Isoamyl Acetate FCC, pentyl acetate, acetone, butanone, ketopentamethylene, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, THF, 1, the 4-dioxane.
6. the compound method of 4-tert-butyl cyclohexyl chloride formic ester according to claim 1, it is characterized in that: the amount of said organic solvent is 10～30 times of 4-tertiary butyl hexalin volume.
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CN106045802B (en) * 2016-06-20 2019-02-01 长江大学 A kind of alicyclic and araliphatic chloro-formate preparation method

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CN101080380A (en) * 2004-10-19 2007-11-28 通用电气公司 Method for the preparation of aliphatic chloroformates

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101080380A (en) * 2004-10-19 2007-11-28 通用电气公司 Method for the preparation of aliphatic chloroformates

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Title
Livius Cotarca 等人.Bis(trichloromethyl)Carbonate in Organic Synthesis.《Synthesis》.1996,第1996卷553－576. *

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