CN107805180A - A kind of preparation method of aryldiazonium chlorocuprate - Google Patents
A kind of preparation method of aryldiazonium chlorocuprate Download PDFInfo
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- CN107805180A CN107805180A CN201711045716.3A CN201711045716A CN107805180A CN 107805180 A CN107805180 A CN 107805180A CN 201711045716 A CN201711045716 A CN 201711045716A CN 107805180 A CN107805180 A CN 107805180A
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- nitrous acid
- chlorocuprate
- aryldiazonium
- ester
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Abstract
The invention provides a kind of preparation method of aryldiazonium chlorocuprate, stable salt is formed using aryl diazonium salts and chlorine copper acid group, original position prepares aryldiazonium chlorocuprate, and complex compound preparation and decomposition are carried out by controlling reaction temperature, it is this to prepare diazol using Examples of non-aqueous solvents, the chlorocuprate of in-situ preparation aryldiazonium again, the method for finally carrying out Sandmeyer using the difference of diazonium salt-stable, can have the function that recovery and emission reduction in actual production.
Description
Technical field
The present invention relates to compound synthesis field, especially a kind of preparation method of aryldiazonium chlorocuprate.
Background technology
Primary amine compound in acid condition, can be reacted with nitrous acid sodium salt, generate diazol.By aliphatic
The diazol of primary amine generation is unstable easily to decompose, and the diazol of primary aromatic amine generation can be deposited stably at low temperature
Reacting generally in 0-5 DEG C of progress.Nonetheless, aryl diazonium salts are to physical factors such as heated, illumination, vibrations, electrostatic
Sensitivity, these factors can trigger diazol that quick and uncontrollable decomposition occurs, and may cause explode (Roe, A.In
Organic Reactions；Adams,R.Ed.,Wiley:New York,1949,Vol 5).
Under the effect of corresponding cuprous halide weight can occur for aromatic diazo hydrochloride or aromatic diazo hydrobromate
Nitrogen base is referred to as Sandmeyer reactions (representativeness summary (a) .Hodgson, H.H.The by chlorine or bromine substitution reaction
Sandmeyer reaction.Chem.Rev.1947,40,251-277.(b)Cowdrey,W.A.,Davies,
D.S.Sandmeyer and related reactions.Quart.Revs.(London)1952,6,358-379.(c)
.Nonhebel,D.C.Copper-catalyzed single-electron oxidations and
reductions.Special Publication-Chemical Society 1970,409-437.(d).Galli,
C.Radical reactions of arenediazonium ions:An easy entry into the chemistry
of the aryl radical.Chem.Rev.1988,88,765-792.).The cyaniding aqueous solutions of potassium of diazol and cuprous cyanide
Acted on, the reaction that diazo is substituted by cyano group, also referred to as Sandmeyer reaction.Cuprous halide, cyanogen are replaced using copper powder
Change cuprous, diazo is transformed into the reaction of corresponding halogen or cyano group, be then referred to as Gattermann reactions.Gatterman
Operation is simple, but in addition to indivedual reactions, yield is typically not so good as to react with Sandmeyer.
Due to aryl diazonium salts less stable, it is anti-typically directly to carry out Sandmeyer after diazotising is carried out to arylamine
Should.In diazo process, reaction is carried out generally in aqueous phase, and the diazol of generation is typically dissolved in water or is partially soluble in water.Instead
Should during, sour dosage is usually 2.5-3 times of arylamine mole and measured, with the acid needed for maintaining during diazo-reaction
Property, and suppress the formation of the accessory substances such as amino azo.The salt that part arylamine is formed with acid, solubility is poor in water, can be
Reacted in organic solvent.The organic solvent used can be the larger organic solvent of polarity, it is conventional have acetic acid, acetone,
N, N-dimethylformamide (DMF) etc..
Best using freshly prepd stannous chloride or cuprous bromide effect in Sandmeyer reactions, the halogenation used is sub-
The mole dosage of copper is typically bigger than the dosage of aryl diazonium salts, i.e., mol ratio is more than 1.Stannous chloride is not soluble in water, but is dissolved in
Concentrated hydrochloric acid, forms blackish green chlorine copper acid, and cuprous bromide is similar.Therefore, in Sandmeyer reactions, the dosage of copper compared with
Greatly, and after reacting the acid waste water generated is, it is necessary to handle and reclaim copper ion, to reach emission request.
Under room ambient conditions, the acidic aqueous solution of chlorine copper acid can not typically make aryl diazonium salts that Sandmeyer occur, and reaction needs
Temperature that will be higher could be reacted.During reaction, by the acidic aqueous solution of cuprous halide at low temperature with aryl diazonium salts
Solution mixes, then is gradually heated to certain reaction temperature and is reacted, and avoids the violent release of nitrogen.
The mechanism of Sandmeyer reactions is not also fully aware of at present, it is generally understood that with cuprous halide list occurs for diazol
Nitrogen is lost after electronics transfer, and forms phenyl radical, and then generates halogenated aryl hydrocarbon.
Obushak, M.O. et al. (Obushak, M.D., Lyakhovych, M.B., Ganushckak,
M.I.Arenediazonium Tetrachlorocuprates(II).Modification of the Meerwein and
Sandmeyer Reactions, Tetrahedron Letters, 1998,39,9567-70) it is found that preparation diazonium chlorine copper acid
The conventional method of salt.Aryl diazonium chloride salt is specifically prepared in aqueous phase, then diazol and ferric chloride reaction are obtained into virtue
Base diazonium tetrachloro closes molysite.By the latter in acetone or alcohol solution, metathesis reaction occurs with copper chloride, aryl is prepared
The chlorocuprate of diazonium.
Obushak et al. find, above-mentioned complex compound is dissolved in DMSO, can trigger Sandmeyer reaction and
Meerwein arylation reactions.When reaction is carried out, the solvent that uses can be with DMSO outside, can also be DMF, water/acetone, water/second
Alcohol etc..Meanwhile the temperature for reacting progress is relatively low, can carry out at room temperature, and yield is preferable, the total recovery of two-step reaction exists
75-91%.
Simultaneously according to document (Meek, D.W., Straub, D.K., Drago, R.S., Transition Metal Ion
Complexes of Dimethyl Sulfoxide, J.Am.Chem.Soc.1960,82,6013-6016) result,
Obushak thinks, is that DMSO forms more stable complex compound with copper, accelerates the decomposition of the chlorocuprate of aryldiazonium four：
Obushak method is carefully studied it can be found that using Obushak methods, is preparing the chlorine copper acid of aryldiazonium
During salt, step is various, and a certain degree of reduction is brought to yield, meanwhile, decomposition explosion after shock also be present in dry diazol
Risk.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of aryldiazonium chlorocuprate.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of aryldiazonium chlorocuprate, including diazotising, generation complex compound and Sandmeyer reactions three
Individual step, diazotising is carried out to arylamine using the nitrous acid ester of lower alcohol in organic phase, then add the solution of copper chloride, original position system
For aryldiazonium chlorocuprate and then Sandmeyer reactions are carried out, it is molten using non-level or low pole higher boiling after reaction terminating
Agent carries out solvent displacement, and the mantoquita added during reaction is recovered by filtration.
Preferably, the preparation method of above-mentioned aryldiazonium chlorocuprate, specific reaction equation are as follows：
During progress is diazotizing, for convenience of in-situ preparation aryldiazonium chlorocuprate, diazo-reaction is organic
Carried out in solvent.To ensure the dissolving as big as possible to aryl nitrogen salt, organic solvent 1 generally selects list more than middle polarity
One solvent or mixed solvent, these solvents are ketone, ethers, esters, alcohols, carboxylic acid, carboxylic acid derivates, sulfone and sulfoxide, heterocycle
Class etc..Such as acetone, tetrahydrofuran (THF), ethyl acetate, ethanol, acetic acid, dimethyl sulfoxide (DMSO), N, N-dimethyl formyl
Amine (DMF) or methyl pyrrolidone.Consider the recovery of solvent and copper compound, avoid using high boiling solvent as far as possible.Reaction
The preferable solvent of middle use is ketone, ethers, alcohols etc., preferably acetone, ethanol.
When carrying out diazotising, nitrosation is carried out using the nitrous acid ester of fatty alcohol as sodium nitrite equivalent.The Asia
Nitrate is nitrous acid methanol ester, nitrous acid ethanol ester, nitrous acid propyl alcohol ester, nitrous acid isopropyl alcohol ester, nitrous acid butyl alcohol ester, Asia
Nitric acid sec-butyl alcohol ester, nitrous acid tert-butyl alcohol ester, nitrous acid amylalcohol ester, nitrous acid isoamyl alcohol ester, nitrous acid tert-pentyl alcohol ester or nitrous
The secondary isoamyl alcohol ester of acid.These nitrous acid ester can use alcohol compound and sodium nitrite prepare in acid condition (MeONO,
Hartung W.H.and Crossley,F.Isonitrosopropiophenone,Organic Syntheses,
Coll.Vol.2,p.363(1943)；Vol.16,p.44(1936).；EtONO,Semon,W.L.and Damerel,
V.R.Dimethylglycoxime,Org.Synth.1930,10,22；Coll.Vol.2,p.204(1943)；BuONO,
isoAmy-ONO,Noyes,W.A.n-Butyl Nitrite,Organic Syntheses,Coll.Vol.2,p.108
(1943)；Vol.16,p.7(1936).)；It can also be prepared using alcohol compound with nitrogen trioxide.In view of nitrous
The toxicity and production cost of ester, in production using preferably nitrous acid methanol ester and nitrous acid ethanol ester, and in laboratory
It is middle to use preferable butyl nitrite and nitrous acid isoamyl alcohol ester.
During diazotising, the temperature of reaction system should be controlled in -10 DEG C -20 DEG C, preferably 0-15 DEG C, most preferably 5-10
℃。
When preparing aryldiazonium chlorocuprate, single or mixed solvent can be used.The selection of organic solvent 2, can be with
Using to the preferable alcohols of chlorination copper dissolution and ketone compounds, wherein preferably alcohols, best methanol and ethanol.
When copper chloride is added into diazol, to avoid reacting violent generation, it should be added dropwise.During addition, reaction temperature
It should control at -10-20 DEG C, preferably 0-15 DEG C, most preferably 5-10 DEG C.
When carrying out Sandmeyer reactions, carried out by the temperature for changing reaction system.The temperature of system should be controlled during reaction
System is between -5-35 DEG C, preferably 10-30 DEG C, most preferably 20-25 DEG C.
Processing stage after the reaction, polar solvent, the height boiling are replaced using high boiling nonpolar or weak polar solvent
The nonpolar or weak polar solvent of point is benzene, toluene, mixed xylenes, single dimethylbenzene, trimethylbenzene, chlorobenzene, single/mixing two
Chlorobenzene or polysubstituted benzene aromatic hydrocarbon, now mantoquita because solubility reduce and separate out, be separated by filtration；After product precipitation, through distillation
Or it is recrystallized to give sterling.
The beneficial effects of the invention are as follows：
The preparation method of above-mentioned aryldiazonium chlorocuprate, stable salt is formed using aryl diazonium salts and chlorine copper acid group,
Original position prepares aryldiazonium chlorocuprate, and carries out complex compound preparation and decomposition by controlling reaction temperature, this using non-aqueous
Phase solvent prepares diazol, then the chlorocuprate of in-situ preparation aryldiazonium, is finally carried out using the difference of diazonium salt-stable
Sandmeyer method, recovery and emission reduction can be haveed the function that in actual production.
Methods described has the following advantages compared with traditional Sandmeyer methods：Technique is simple, easy to operate, bar
Part is gentle, and yield is preferable, is easily handled；In course of reaction, using non-aqueous system, the cost of wastewater treatment is eliminate or reduced；
During post-reaction treatment, the recovery method of mantoquita is easy, efficient, avoids a large amount of high-concentration copper-containing waste water in traditional handicraft
Processing.
Embodiment
Technical scheme of the present invention is further described with reference to specific embodiment.
Embodiment 1
2-methylaniline hydrochlorides of 7.2g, 30ml acetone are added into 100ml there-necked flasks, ice-water bath is cooled to 0 DEG C.Drop
Add 8.8g isoamyl alcohol nitrous acid ester, process system heating is added dropwise, controls rate of addition, 0-15 DEG C of temperature control.It is added dropwise, 2-methyl
Anilinechloride dissolves, and system is in light yellow.
5.0g copper chlorides are dissolved in 30ml ethanol, are added drop-wise in above-mentioned system, control rate of addition, temperature is less than 5 DEG C.Drop
During adding, system has yellow solid precipitation, and color burn, system becomes viscous when adding 1/3rd, with copper chloride ethanol
The dropwise reaction system of solution is in yellow green.It is added dropwise, 20min is reacted under ice-water bath, is gradually warming up to room temperature and reaction 2 is small
When, system becomes blackish green by yellow green.
Using 50ml toluene, precipitation is rotated, green solid is separated out, filtering, obtains 5.0g；Distillation, collect 154-158 DEG C of fraction
5.5g, yield 87%.
Reference examples
Ref：Marvel and,C.S.McElvain,o-chlorotoluene and p-chlorotoluene
S.M.Org.Synth.1923,3,33。
12.50g (0.05mol) copper sulphate, 3.25g sodium chloride are dissolved in 40ml hot water.Sodium sulfite solution：2.65g
Sodium hydrogensulfite, 1,75g sodium hydroxides, are dissolved in 20ml water.Sodium sulfite solution is added drop-wise in above-mentioned solution, 5- is added dropwise
10min, it is cooled to room temperature.With decantation cleaning product.White powder is obtained, is kept in dark place.Half product is taken to be dissolved in 20g hydrochloric acid
(28%) in.
10g hydrochloric acid (28%), 2.14g ortho-aminotoluenes (0.02mol) are added into 100ml round-bottomed flask.Mixture is cold
But to 0 DEG C of precipitation fine particle.Stirring is started, stops cryostat, 1.40g natrium nitrosums is added and is dissolved in 4ml water.Diazotising needs
Maintain 0-5 DEG C of reaction 50min.Cuprous chloride solution is cooled to 0 DEG C when diazotising.
Cold diazo solution is poured into rapidly in the cuprous chloride solution being stirred vigorously.Solution becomes more sticky, and reason is
Because the addition compound product that diazol and stannous chloride are formed separates out.Reaction system is warmed to room temperature, and continues to stir 1.5-3h.Work as temperature
Rise to 15 DEG C of addition compound products and become unstable, produce nitrogen and ortho-chlorotolu'ene.60 DEG C are warming up in the defined time again, allows addition
Product fully decomposes.Ortho-chlorotolu'ene is on the upper strata of copper salt solution.Steam distillation, product washing are carried out, calcium chloride is dried.
3.75g products, yield 74%.
Embodiment 2
6.5g anilinechlorides, 30ml acetone are added into 100ml there-necked flasks, ice-water bath is cooled to 0 DEG C.It is different that 8.8g is added dropwise
Amylalcohol nitrous acid ester, process system heating is added dropwise, controls rate of addition, 0-15 DEG C of temperature control.It is added dropwise, anilinechloride is molten
Solution, system is in light yellow.
5.0g copper chlorides are dissolved in 30ml ethanol, are added drop-wise in above-mentioned system, control rate of addition, temperature is less than 10 DEG C.
During dropwise addition, system has yellow solid precipitation, and color burn, system becomes viscous when adding 1/3rd, with copper chloride second
The dropwise reaction system of alcoholic solution is in yellow green.It is added dropwise, 20min is reacted under ice-water bath, is gradually warming up to room temperature and reaction 2
Hour, system becomes blackish green by yellow green.
Using 50ml toluene, precipitation is rotated, green solid is separated out, filtering, obtains 4.9g；Distillation, collect 128-130 DEG C of fractions
4.9g, yield 88%.
Embodiment 3
9.4g methyl anthranilates hydrochloride, 30ml acetone are added into 100ml there-necked flasks, ice-water bath is cooled to 0
℃.8.8g isoamyl alcohol nitrous acid ester is added dropwise, process system heating is added dropwise, controls rate of addition, 0-15 DEG C of temperature control.It is added dropwise,
Methyl anthranilate hydrochloride salt, system is in light yellow.
5.0g copper chlorides are dissolved in 30ml ethanol, are added drop-wise in above-mentioned system, control rate of addition, temperature is less than 10 DEG C.
During dropwise addition, system has yellow solid precipitation, and color burn, system becomes viscous when adding 1/3rd, with copper chloride second
The dropwise reaction system of alcoholic solution is in yellow green.It is added dropwise, 20min is reacted under ice-water bath, is gradually warming up to 20 DEG C and reaction 2
Hour, system becomes blackish green by yellow green.
Using 50ml toluene, precipitation is rotated, green solid is separated out, filtering, obtains 5.0g；Distillation, collect 108 DEG C/30mmHg
Fraction 6.8g, yield 80%.
The above-mentioned detailed description carried out with reference to embodiment to a kind of preparation method of aryldiazonium chlorocuprate, is explanation
Property rather than it is limited, can include several embodiments according to limited scope, therefore of the invention overall not departing from
Changing and modifications under design, should belong within protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of aryldiazonium chlorocuprate, it is characterised in that：Including diazotising, generation complex compound and Sandmeyer reacts three steps, and diazotising, then chlorination are carried out to arylamine using the nitrous acid ester of lower alcohol in organic phase The solution of copper, original position prepare aryldiazonium chlorocuprate and then carry out Sandmeyer reactions, after reaction terminating using non-level or Low pole high boiling solvent carries out solvent displacement, and the mantoquita added during reaction is recovered by filtration.
- 2. the preparation method of aryldiazonium chlorocuprate according to claim 1, it is characterised in that：Specific reaction equation is such as Under：Carry out it is diazotizing during, diazo-reaction is carried out in organic solvent, the organic solvent 1 be ketone, ethers, Esters, alcohols, carboxylic acid, carboxylic acid derivates, sulfone and sulfoxide or heterocyclic；When carrying out diazotising, nitrosation, the nitrous acid are carried out using the nitrous acid ester of fatty alcohol as sodium nitrite equivalent Ester is nitrous acid methanol ester, nitrous acid ethanol ester, nitrous acid propyl alcohol ester, nitrous acid isopropyl alcohol ester, nitrous acid butyl alcohol ester, nitrous acid Sec-butyl alcohol ester, nitrous acid tert-butyl alcohol ester, nitrous acid amylalcohol ester, nitrous acid isoamyl alcohol ester, nitrous acid tert-pentyl alcohol ester or nitrous acid are secondary Isoamyl alcohol ester, the temperature of reaction system should be controlled at -10 DEG C -20 DEG C during diazotising；When preparing aryldiazonium chlorocuprate, organic solvent 2 is to the preferable alcohols of chlorination copper dissolution and ketone compounds；Copper chloride is added dropwise into diazol, reaction temperature is controlled at -10-20 DEG C；When carrying out Sandmeyer reactions, instead The temperature control of seasonable system is between -5-35 DEG C；Processing stage after the reaction, polar solvent is replaced using high boiling nonpolar or weak polar solvent, it is described high boiling Nonpolar or weak polar solvent is benzene, toluene, mixed xylenes, single dimethylbenzene, trimethylbenzene, chlorobenzene, single/mixed dichlorobenzene Or polysubstituted benzene aromatic hydrocarbon, now mantoquita because solubility reduce and separate out, be separated by filtration；After product precipitation, through distilling or again Crystallization obtains sterling.
- 3. the preparation method of aryldiazonium chlorocuprate according to claim 2, it is characterised in that：The organic solvent 1 For acetone or alcohol.
- 4. the preparation method of aryldiazonium chlorocuprate according to claim 2, it is characterised in that：The nitrous acid ester is Nitrous acid methanol ester, nitrous acid ethanol ester, butyl nitrite or nitrous acid isoamyl alcohol ester.
- 5. the preparation method of aryldiazonium chlorocuprate according to claim 2, it is characterised in that：Reactant during diazotising The temperature of system should be controlled at 5-10 DEG C.
- 6. the preparation method of aryldiazonium chlorocuprate according to claim 2, it is characterised in that：The organic solvent 2 For methanol and ethanol.
- 7. the preparation method of aryldiazonium chlorocuprate according to claim 2, it is characterised in that：Added into diazol The reaction temperature of copper chloride is controlled at 5-10 DEG C.
- 8. the preparation method of aryldiazonium chlorocuprate according to claim 2, it is characterised in that：Carry out When Sandmeyer reacts, the temperature control of system is at 20-25 DEG C during reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086988A (en) * | 1965-04-05 | 1967-10-11 | Gevaert Photo Prod Nv | Hydrazine compounds |
| EP0353600A2 (en) * | 1988-08-01 | 1990-02-07 | Hitachi, Ltd. | Aromatic diazonium salt, radiation sensitive composition containing the aromatic diazonium salt and method for formation of pattern using the radiation sensitive composition |
| CN107056621A (en) * | 2012-04-26 | 2017-08-18 | 拜耳作物科学股份公司 | The method for preparing N (isopropyl benzyl of 5 chlorine 2) cyclopropylamine |
-
2017
- 2017-10-31 CN CN201711045716.3A patent/CN107805180A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086988A (en) * | 1965-04-05 | 1967-10-11 | Gevaert Photo Prod Nv | Hydrazine compounds |
| EP0353600A2 (en) * | 1988-08-01 | 1990-02-07 | Hitachi, Ltd. | Aromatic diazonium salt, radiation sensitive composition containing the aromatic diazonium salt and method for formation of pattern using the radiation sensitive composition |
| CN107056621A (en) * | 2012-04-26 | 2017-08-18 | 拜耳作物科学股份公司 | The method for preparing N (isopropyl benzyl of 5 chlorine 2) cyclopropylamine |
Non-Patent Citations (3)
| Title |
|---|
| MYKOLA D OBUSHAK等: "Arenediazonium Tetrachlorocuprates(II). Modification of the Meerwein and Sandmeyer Reactions", 《TETRAHEDRON LETTERS》 * |
| N. D. OBUSHAK等: ""Arenediazonium Tetrachlorocuprates(II). Modified Versions of the Meerwein and Sandmeyer Reactions", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| 何浩明: "新法回收Sandmeyer反应中的氯化亚铜", 《江苏化工》 * |
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