CN105237363B - The preparation method of 2 (4 tert-butyl benzene epoxide) Hexalin - Google Patents
The preparation method of 2 (4 tert-butyl benzene epoxide) Hexalin Download PDFInfo
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- CN105237363B CN105237363B CN201510795097.4A CN201510795097A CN105237363B CN 105237363 B CN105237363 B CN 105237363B CN 201510795097 A CN201510795097 A CN 201510795097A CN 105237363 B CN105237363 B CN 105237363B
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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Abstract
The present invention is for problem present in the preparation of current propargite active compound intermediate 2 (4 tert-butyl benzene epoxide) Hexalin, there is provided a kind of preparation method of 2 (4 tert-butyl benzene epoxide) Hexalin.The present invention due to steric effect, is almost generated without isomer, substantially increases the content of intermediate 2 (4 tert-butyl benzene epoxide) Hexalin using alkylation again after first and phenol condensation.2 (4 tert-butyl benzene epoxide) Hexalin of the invention adopts phenol for raw material, first it is condensed with 7-oxa-bicyclo[4.1.0, alkylation phenyl ring on is carried out again, due to replacing the steric hindrance of butylcyclohexyl to strengthen, the generation of ortho position and meta alkylation isomer is avoided, so as to improve the content of product.
Description
Technical field
The invention belongs to technical field of pesticide, and in particular to acaricide technical field of pesticide, more particularly to a kind of propargite
The preparation method of active compound intermediate high-load aromatic ring alcohol.
Background technology
Propargite (Propargite) also known as propargite, the third propargite, chemical name are 2- (4- tert-butyl benzene oxies)-ring
Base Propargyl sulfite, belongs to organosulfur acaricide containing wide spectrum, to having specially good effect into demodicid mite and deutonymph, can be used for preventing and treating Cotton Gossypii,
The various evil mites of vegetable, Fructus Mali pumilae, mandarin orange, tea, flowers and other crops, to most natural enemies securities.Propargite effect extensively, can be killed multiple
Evil mite, can also kill the evil mite developed immunity to drugs by other insecticides, no matter it is equal to kill into demodicid mite, deutonymph, young demodicid mite and demodicid mite ovum effect
Preferably, more than 30 years is used in the world, drug-fast problem that so far there are no.Propargite has selectivity, to Apiss and
Natural enemy is safer, and persistently, toxicity is very low for residual effect, little to people and animals and natural environment harm, is the preferable acaricide of integrated control.I
State starts from the 1980s to the research of propargite, and late nineteen eighties start to put into commercial production, and the present country has 2
Manufacturer, annual production is at 2000 tons or so.Patent of invention ZL 200610012554.9 discloses that " content is for 93%-96%
The preparation method of propargite active compound ", its synthetic route are with p-t-butyl phenol as raw material, through generating with HEO reaction
P tert Butylphenoxycyclohexanol, then 2- (4- tertiary butyls) cyclohexyl chloride sulfite is generated with thionyl chloride reaction, by adding
Excess thionyl chloride is removed by the inerts such as petroleum ether under a high vacuum, after the thionyl chloride of residual is taken off, then
Propargite active compound of the content for 93%-96% is obtained with propilolic alcohol through condensation reaction.The invention mainly solves propargite active compound
In building-up process, thionyl chloride is difficult to the problem for removing.
Wherein, 2- (4- tert-butyl benzene epoxides) Hexalin is the key intermediate in the synthesis of propargite active compound, and its quality is straight
Connect the quality for affecting propargite active compound.Therefore 2- (the 4- tert-butyl benzene epoxides) Hexalin of production high-load is into domestic enterprise
The problem of research.At present, domestic 2- (4- tert-butyl benzene epoxides) Hexalin synthesis is mostly using p-t-butyl phenol and epoxide ring
Hexane is initiation material, obtains after being condensed, being acylated, be condensed again.The synthetic route response time is longer at present, content yield
Low, its main cause is：Under the reaction conditions, the micro ortho position that contains in p-t-butyl phenol and meta-isomer affect
The purity of intermediate.
Additionally, phase transfer catalysis process synthesizes technical study (Zheng Zhiming, Li Lixin, Yu's antiperspirant of P tert Butylphenoxycyclohexanol
Soldier etc., fine-chemical intermediate, calendar year 2001, the 6th phase of volume 31) disclose a kind of synthetic method of tert-butyl benzene oxygen Hexalin.
The method with p-t-butyl phenol as raw material, with water and toluene as reaction medium, in the presence of phase transfer catalyst (PTC) with
7-oxa-bicyclo[4.1.0 reacts, and its reaction equation is：
However, the method cannot also exclude the micro ortho position contained in p-t-butyl phenol and meta-isomer in the reaction
Impact of the by-product of generation to intermediate 2- (4- tert-butyl benzene epoxides) hexamethylene alcohol content, so that further have influence on propargite
The quality of active compound.
Content of the invention
The present invention is directed to present in the preparation of current propargite active compound intermediate 2- (4- tert-butyl benzene epoxides) Hexalin and asks
Topic, there is provided the preparation method of a kind of 2- (4- tert-butyl benzene epoxides) Hexalin.The present invention using first with phenol condensation after alkane again
Base, due to steric effect, almost generates without isomer, substantially increases intermediate 2- (4- tert-butyl benzene epoxides) Hexalin
Content.
Technical scheme：The preparation method of 2- (4- tert-butyl benzene epoxides) Hexalin, comprises the following steps：First
First, phenol and 7-oxa-bicyclo[4.1.0 condensation reaction, obtain 2- (phenoxy group) Hexalin；Then 2- (phenoxy group) Hexalin and the tert-butyl group
Chlorine carries out Friedel-Crafts reaction, obtains 2- (4- tert-butyl benzene epoxides) Hexalin.
Preferably, the preparation method of 2- (4- tert-butyl benzene epoxides) Hexalin, comprises the following steps：(1) condensation reaction：
Phenol, 7-oxa-bicyclo[4.1.0 and catalyst I are added in reactor, heating for dissolving, be condensed under 100-102 DEG C of temperature conditionss anti-
4-5 hours are answered, after product is separated, 2- (phenoxy group) Hexalin is obtained；As shown in Eq.1；
(2) alkylated reaction：Catalyst II, 1,2- dichloroethanes are added into intermediate 2- (phenoxy group) Hexalin kettle,
Hydrogen chloride gas are passed through under 15-20 DEG C of temperature conditionss 0.5 hour；Ventilation finishes rear Deca tertiary butyl chloride, at 15-25 DEG C
0.5-1.5 hours are reacted under the temperature conditionss of (20 DEG C), obtain 2- (4- tert-butyl benzene epoxides) Hexalin after product is separated；Such as
Shown in Eq.2；
Wherein, the catalyst I described in step (1) is strong basicity catalyst series, preferably sodium hydroxide, potassium hydroxide, first
Any one in sodium alkoxide, Sodium ethylate；The catalyst I：Phenol：Mol ratio=the 0.04-0.05 of 7-oxa-bicyclo[4.1.0:1：1；Step
Suddenly the catalyst II described in (2) is Lewis acid catalyst series, preferably in aluminum chloride, ferric chloride, zinc chloride or sulphuric acid
Any one；The catalyst II：Tertiary butyl chloride=0.04-0.05:1.
Product separation described in step (1) is comprised the following steps：Toluene and water, adjustment is added in the product of condensation reaction
PH value is washed 2-3 time to 7-8；Water is extracted once with toluene, merges oil phase, precipitation obtains 2- (phenoxy group) Hexalin；Step
(2) the product separation described in is comprised the following steps：Add water in the product of alkylated reaction and wash 2-3 time, then oil phase precipitation, obtains
2- (4- tert-butyl benzene epoxides) Hexalin.Described 2- (4- tert-butyl benzene epoxides) hexamethylene alcohol content >=99%, yield is with phenol
Meter >=98%.The all of raw material that the present invention is adopted all is commercially available industrial products.
Be will be rearmounted for phenol tert-butylation the key point of the present invention, it is to avoid isomer generation, improves intermediate and contains
Amount.Its principle is described by taking alkylation of phenol as an example：In the synthesis of 2- (4- tert-butyl benzene epoxides) Hexalin, generally using to the tert-butyl group
Phenol is raw material；And domestic p-t-butyl phenol is generally got by alkylation of phenol, alkylation of phenol is that electrophilic on aromatic ring takes
Generation reaction, hydroxyl mainly obtain ortho para product as first kind substituent group, and the alkyl in substituent group makes aromatic ring further live again
Change, easily generate many alkyl products.And 2- (4- tert-butyl benzene epoxides) of the present invention Hexalin adopts phenol for raw material, elder generation and epoxide ring
Hexane is condensed, then carries out the alkylation on phenyl ring, due to replacing the steric hindrance of butylcyclohexyl to strengthen, it is to avoid ortho position and meta
The generation of alkylation isomer, so that improve the content of product.
The beneficial effects of the present invention is：(1) 2- (4- tert-butyl benzene epoxides) the hexamethylene alcohol content that prepared by the present invention high (>=
99%)；High income, total recovery >=98% (in terms of phenol).(2) alkylation, cleverly using the steric effect of cyclohexyl, keeps away afterwards
Exempt to generate isomer, reduce by-product and generate, so as to the product of output high-load.
Specific embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1：
(1) it is condensed：In the reactor of 100L, by 37.40kg phenol (>=99%, 394mol), 39.00kg epoxy hexamethylenes
Alkane (>=99%, 394mol), 0.82kg sodium hydroxide (>=96%, 19.7mol) are put in reactor after metering, are risen under stirring
Temperature is incubated 0.5 hour, is allowed to dissolve, is continuously heating to 100-102 DEG C to 55-60 DEG C, and insulation 4-5 hours carry out condensation reaction.
(2) neutralize：After the completion of condensation reaction, in reactor, 40L toluene (>=99%, 376mol) 25L water is added, continued
Lower Deca 1.0kg sulphuric acid (>=98%, 9.85mol) of stirring, completion of dropping stand 0.5 hour after stirring 0.5 hour, carry out point
Layer, lower floor's oil phase are gone back in kettle, and water is mutually standby, and oil phase adds 25L water to be repeated to wash hierarchical operations, and oil phase is gone back in kettle, and two
Add 20L toluene (>=99%, 186mol) to be extracted in secondary water phase, merge oil phase precipitation, purify toluene and water, obtain centre
Body 2- (phenoxy group) Hexalin.
(3) alkylation：Into intermediate 2- (phenoxy group) Hexalin kettle, input 1,2- dichloroethanes 40L (>=99%,
508mol), 3.20kg anhydrous ferric trichlorides (>=99%, 19.7mol), stirring are cooled to 15-20 DEG C, lead to hydrogen chloride gas 0.5
Hour；Ventilation is finished, at this temperature Deca 36.5kg tertiary butyl chloride (>=99%, 394mol), time for adding 2 hours；Deca
Finish, insulation at 20 DEG C carries out tertiary butyl reaction in 1 hour.After reaction terminates, wash 2-3 time, add water 25L every time, and oil phase enters
Row precipitation, purifies dichloroethanes and water, obtains 2- (4- tert-butyl benzene epoxides) Hexalin 96.92Kg, content 99.3%, yield
98.5% (in terms of phenol).The raw material adopted in preparation process is commercially available prod.
Embodiment 2：
As different from Example 1, in step (1) condensation reaction, adopt potassium hydroxide for catalyst I, weight is
0.92kg (>=96%, 15.76mol)；In step (3) alkylated reaction, adopt aluminum chloride for catalyst II, weight is
2.39kg (>=99%, 17.73mol)；After tertiary butyl chloride completion of dropping, insulation at 25 DEG C carries out tertiary butyl reaction in 0.5 hour.
Other steps are same as Example 1, finally give 2- (4- tert-butyl benzene epoxides) Hexalin 96.62kg, content 99.1%, yield
98.1% (in terms of phenol).
Embodiment 3：
As different from Example 1, in step (1) condensation reaction, Feldalat NM is 0.97kg (>=99%, 17.73mol)；
In step (3) alkylated reaction, zinc chloride is adopted for catalyst II, weight is 2.17kg (>=99%, 15.76mol)；The tert-butyl group
After chlorine completion of dropping, insulation at 15 DEG C carries out tertiary butyl reaction in 1.5 hours.Repeat to implement by described identical step
Example 1, obtains 2- (4- tert-butyl benzene epoxides) Hexalin 96.43kg, content 99.3%, yield 98.0% (in terms of phenol).
Embodiment 4：
As different from Example 1, in step (1) condensation reaction, Sodium ethylate is 1.21kg (>=99%, 17.73mol)；
In step (3) alkylated reaction, sulphuric acid is adopted for catalyst II, weight is 1.58kg (>=98%, 15.76mol)；Tertiary butyl chloride
After completion of dropping, insulation at 18 DEG C carries out tertiary butyl reaction in 1.2 hours.Repeat embodiment by described identical step
1, obtain 2- (4- tert-butyl benzene epoxides) Hexalin 96.83kg, content 99.3%, yield 98.4% (in terms of phenol).
Embodiment 5：Comparative example
Repeat embodiment 1 by described identical step, but raw material phenol is used in step (1) condensation reaction
Substitute with mole p-t-butyl phenol, cancellation step (3) obtains 2- (4- tert-butyl benzene epoxides) Hexalin 96.50kg, and content is
96.6%, yield is 95.4%.The raw material adopted in preparation is commercially available prod, and remaining is with embodiment 1.
Claims (5)
- The preparation method of 1.2- (4- tert-butyl benzene epoxides) Hexalin, it is characterised in that：Comprise the following steps：First, phenol and 7-oxa-bicyclo[4.1.0 condensation reaction, obtains 2- (phenoxy group) Hexalin；Then 2- (phenoxy group) Hexalin carries out Fu with tertiary butyl chloride Gram reaction, obtain 2- (4- tert-butyl benzene epoxides) Hexalin.
- 2. the preparation method of 2- (4- tert-butyl benzene epoxides) Hexalin according to claim 1, it is characterised in that：Including with Lower step：(1) condensation reaction：Phenol, 7-oxa-bicyclo[4.1.0 and catalyst I are added in reactor, heating for dissolving, in 100-102 DEG C temperature conditionss under condensation reaction 4-5 hours, will product separate after obtain 2- (phenoxy group) Hexalin；As shown in Eq.1；(2) alkylated reaction：Catalyst II and 1,2- dichloroethanes are added into intermediate 2- (phenoxy group) Hexalin kettle, Hydrogen chloride gas are passed through under 15-20 DEG C of temperature conditionss；Ventilation finishes rear Deca tertiary butyl chloride, in 15-25 DEG C of temperature conditionss Lower reaction 0.5-1.5 hours, obtain 2- (4- tert-butyl benzene epoxides) Hexalin after product is separated；As shown in Eq.2；
- 3. the preparation method of 2- (4- tert-butyl benzene epoxides) Hexalin according to claim 2, it is characterised in that：Step (1) the catalyst I described in be strong basicity catalyst series, the catalyst I：Phenol：Mol ratio=the 0.04- of 7-oxa-bicyclo[4.1.0 0.05:1：1；Catalyst II described in step (2) is Lewis acid catalyst series, the catalyst II：Tertiary butyl chloride= 0.04-0.05:1.
- 4. the preparation method of 2- (4- tert-butyl benzene epoxides) Hexalin according to claim 3, it is characterised in that：Step (1) the catalyst I described in is any one in sodium hydroxide, potassium hydroxide, Feldalat NM and Sodium ethylate；Described in step (2) Catalyst II is any one in aluminum chloride, ferric chloride, zinc chloride and sulphuric acid.
- 5. the preparation method of 2- (4- tert-butyl benzene epoxides) Hexalin according to claim 2, it is characterised in that：Step (1) the product separation described in is comprised the following steps：To in the product of condensation reaction, add toluene and water, adjustment pH value to wash to 7-8 Wash 2-3 time；Water is extracted once with toluene, merges oil phase, precipitation obtains 2- (phenoxy group) Hexalin；Product described in step (2) Thing separation is comprised the following steps：Add water in the product of alkylated reaction and wash 2-3 time, then oil phase precipitation, obtains 2- (the 4- tert-butyl groups Phenoxy group) Hexalin.
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| 1,2-环氧环己烷的制备与应用进展;张进等;《化学推进剂与高分子材料》;20141231;第12卷(第6期);第50-57页 * |
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