Method for synthesizing alpha-bromoketone and coproducing bromohydrocarbon

Abstract

The invention discloses a method for synthesizing alpha-bromoketone and coproducing

bromohydrocarbon. The technical scheme comprises the following steps of: adding arylalkyl ketone
compounds, alcohol or epoxy compounds and water into a flask first; dripping bromine into the flask
slowly under the conditions of stirring and heating; performing a bromo-reaction on the bromine and
the ketone compounds to obtain alpha-bromoketone and bromine hydride; dissolving the bromine
hydride in the water to form hydrobromic acid; performing a reaction on the hydrobromic acid and the
alcohol or epoxy compounds to obtain bromohydrocarbon ketone compounds; after the reaction is
completed, performing steam distillation to obtain a raffinate serving as an alpha-bromoketone crude
product after distillation; cooling for separating crystals out; washing and drying the crystals to obtain an
alpha-bromoarylalkyl ketone product; separating an aqueous layer from a distillate serving as a
bromohydrocarbon crude product; washing an organic layer until the organic layer is neutral; drying by
using anhydrous calcium chloride; and distilling to obtain a bromohydrocarbon product. In the method,
the water is taken as a solvent, and the bromohydrocarbon is coproduced while the alpha-bromoketone
compounds are synthesized; and the gross products of the reaction are the alpha-bromoketone, the
bromohydrocarbon and the water, so the method has the characteristics that: the high atom utilization
rate of the reaction is high, the generation or the discharging of noxious substances such as bromine
hydride gas, strong acid waste water and the like is avoided, and the effects of environmental protection,
energy conservation and reduction emission are achieved.

CN101948374B

China

Download PDF

Find Prior Art

Similar

Other languages

Chinese

Inventor

张书文

李志云
Worldwide applications

2010 CN

Application CN 201010245594 events

2010-08-05

Application filed by 河北大学

2010-08-05

Priority to CN 201010245594

2011-01-19

Publication of CN101948374A

2013-08-14

Application granted

2013-08-14

Publication of CN101948374B

Info

Patent citations (1)

Non-patent citations (8)

Cited by (3)

Legal events

Similar documents

Priority and Related Applications

External links

Espacenet

Global Dossier
 Discuss

Description

The method of a kind of synthetic alpha-brominated ketone and coproduction hydrobromic ether

Technical field

The present invention relates to the synthetic field of organic chemical industry, the method for
especially a kind of synthetic alpha-brominated ketone and coproduction hydrobromic ether.

Background technology

Alpha-brominated ketone compound is the very important chemical intermediate of synthetic multiple
medicine, agricultural chemicals, dyestuff, and along with the continuous expansion of its Application
Areas, people also more and more pay attention to the research of its synthetic method.Summing up the
domestic and international research present situation, all is to synthesize by alpha-brominated reaction
with different bromizating agents in different organic solvents usually.The lime light of these researchs is
uses of bromizating agent, and does not pay general attention aspect solvent for use.Up to the present,
Chang Yong bromizating agent mainly contains bromine, cupric bromide, solid-state bromine and closes
mixture, TBuA perbromide, phenyl TMA (TriMethylAmine) perbromide, bromo-succinimide, bromo-
trichloromethane of 1: 1: 1 type mixture of dioxane, pyridine and Hydrogen bromide and bromine,
anhydrous alchlor and zinc bromide etc.; Organic solvent commonly used comprises methyl alcohol or
ethanol, acetic acid, ether, dioxane, chloroform, ethylene dichloride, ethyl acetate, benzene etc.,
specifically referring to following document:

1. Yang Chun dragon, in the person of outstanding talent, Liu YanBing etc. [fine chemistry industry 2004,2
(2) 153-156] have reported that making bromizating agent with bromine carries out the method that
bromo prepares alpha-brominated ketone compound in various organic solvents.

2. open and compete, Chen Shengzong, Wu Can etc. [chemistry world, 2003,2,91-93] have reported that
making bromizating agent with bromine is that catalyzer carries out the method that bromo prepares
alpha-brominated ketone compound with aluminum chloride and zinc bromide in acetic acid.

3. Hu Aixi, Chen Ping, Zheng Yang etc. [Chinese pharmaceutical chemistry magazine, 2002,12 (6) 340-
343] have reported with cupric bromide and have made bromizating agent, carry out the method that
bromo prepares alpha-brominated ketone compound in ethanol or ethyl acetate.

4. Hu Weiwu, Chen Hongyan [chemical industry progress, 2003,22 (3) 287-289] has reported that making
bromizating agent with 1: 1: 1 mixture of pyridine, Hydrogen bromide and bromine carries out the
method that bromo prepares alpha-brominated ketone compound in chloroform.

5.Jong, C.L, Hyun, J.P[Synthet ic Communications, 2007,37 (1), 87-90] reported with NBS and made
bromizating agent, in organic solvent, carry out the method that bromo prepares alpha-brominated
ketone compound.

6.Zang, S.J, Le, C.G[Youji Huaxue, 2007,37 (1), 87-90] reported with tribromide-1-butyl-3-
Methylimidazole and be bromizating agent, in organic solvent, carry out the method that bromo
prepares alpha-brominated ketone compound.

7.Satya.P Varinder.G, Rajive.G etc. [Tetrahedron Letters, 2003,44 (3), 439-442] have reported with the
dibromo dioxane and made the method that bromo that bromizating agent carries out prepares alpha-
brominated ketone compound in organic solvents.

8.Kawano.T, Kato.N[Chemistry Letters, 2006,35 (3), 270-271] reported with the tribromide 4-butyl amine
and carried out the method that bromo prepares alpha-brominated ketone compound as bromizating
agent.

Though a lot of improvement have been done in above-mentioned research aspect bromizating agent,
employed solvent is still organic compound, therefore like inadequate, is summarized as follows:

(1). used a large amount of organic solvents, the toxicity that these solvents have is very strong, and
environmental pollution is serious; Even the very low highly volatile of the boiling point that has causes
combustion explosion, industrial production exists great safety problem.(2). aspect the selection of
bromizating agent, though use cupric bromide can avoid the intense stimulus of bromine, and operate
more conveniently, can produce a large amount of by product bromize alpha ketones, and the utilization
ratio of bromine also has only 50%; Solid-state bromine closes dioxane, pyridine and Hydrogen bromide
and bromine 1: 1: though 1 mixture etc. are more convenient when bromination, but will use bromine
and other compounds to be prepared in advance; Not only preparation cost is higher as for the
perbromide of quaternary ammonium, and also dangerous when using.

It is that bromizating agent carries out the method that bromo prepares alpha-brominated ketone
compound in the presence of sodium bisulfite with bromate that Chinese patent CN101462935A
discloses a kind of, though this method with water as solvent, use a large amount of bromates and
hydrosulphite.It is that bromizating agent is that solvent carries out the method that bromo prepares
alpha-brominated ketone compound with water with bromine that Chinese patent CN1807382A
discloses a kind of, though its water is as solvent, but the utilization ratio of bromine has only 50%, and
other 50% has then generated hydrogen bromide, but does not do any processing in this patent.

Summary of the invention

The technical problem to be solved in the present invention provides the method for a kind of synthetic
alpha-brominated ketone and coproduction hydrobromic ether, be that solvent, bromine are bromo
agent and the synthetic alpha-brominated ketone compound of ketone compounds reaction with water,
and coproduction hydrobromic ether, the utilization ratio of bromine is near 100%, avoid the generation
of bromize hydrogen gas and strongly acid wastewater simultaneously, utilize reaction raw materials to
greatest extent and economize on resources, reduce production costs and increase economic efficiency.

The method and technology scheme of this synthetic alpha-brominated ketone and coproduction
hydrobromic ether comprises: add aryl alkyl ketone compound in the flask earlier, alcohols or epoxy
compounds and water, under stirring and heating condition, slowly be added drop-wise to bromine in
the flask, bromine and ketone compounds carry out bromo-reaction, generate alpha-brominated ketone
and hydrogen bromide, and the water-soluble formation Hydrogen bromide of hydrogen bromide reacts
with alcohols or epoxy compounds again, generate the brominated hydrocarbons compound, reaction
expression is:

Alcohols or the epoxy compounds of the Y representative in the reaction expression, X-Br representative
and product hydrobromic ether thereof;

Carry out wet distillation after reacting completely, the raffinate in the flask of distillation back is alpha-
brominated ketone crude product, separates out crystallization after the cooling, filters, and filtrate is
returned the conduct solvent of batch reaction down; Crystal obtains the alpha-brominated aryl alkyl
ketone of product after washing, drying;

Distillate is the hydrobromic ether crude product, and standing demix divides water-yielding stratum,
and water, 5% yellow soda ash and water washing are to neutral successively for organic layer, and the
Calcium Chloride Powder Anhydrous drying obtains hydrobromic ether through distillation again.

In the method for described synthetic alpha-brominated ketone and coproduction hydrobromic ether,
the employed aryl alkyl ketone compound of synthetic alpha-brominated ketone is selected:

The alpha-brominated aryl alkyl ketone of the product that obtains has following general structure
respectively:

R in the formula be hydrogen atom, (o, m, p)-nitro, 2.4-dinitrobenzene, (o, m, p)-hydroxyl, (o, m, p)-
fluorine, (o, m, p)-chlorine, 2.4-dichloro, (o, m, p)-bromine, (o, m, p)-iodine, (o, m, p)-acetoxyl group, (o,
m, p)-and carboxyl, (o, m, p)-alkoxyl group, (o, m, p)-acetamido, (o, m, p)-and sulfonic group, groups such
as p-phenyl; R 1Be hydrogen atom, 4 alkyl below the carbon.

In the method for described synthetic alpha-brominated ketone and coproduction hydrobromic ether,
the employed alcohols of coproduction hydrobromic ether or epoxy compounds are selected:

The product hydrobromic ether that obtains has following general structure respectively:

HO-(CH 2) n-CH 2Br；

R in the formula be hydrogen atom, (o, m, p)-nitro, 2.4-dinitrobenzene, (o, m, p)-hydroxyl, (o, m, p)-
fluorine, (o, m, p)-chlorine, 2.4-dichloro, (o, m, p)-bromine, (o, m, p)-iodine, (o, m, p)-acetoxyl group, (o,
m, p)-carboxyl, (o, m, p)-alkoxyl group, (o, m, p)-acetamido, (o, m, p)-sulfonic group or p-phenyl; R 1Be
hydrogen atom, 4 alkyl below the carbon; R 2, R 3And R 4Can be hydrogen atom, phenyl or general
molecular formula C nH 2n+1The following alkyl of 13 carbon atoms; R 5And R 6Can be hydrogen atom,
general molecular formula C nH 2n+1The following alkyl of 13 carbon atoms; N=1～4 integers such as
grade.
In the method for described synthetic alpha-brominated ketone and coproduction hydrobromic ether,
aryl alkyl ketone, the mol ratio of bromine and alcohols or epoxy compounds is 1: 1: 1, is 1～1.5: 1 as the
water of solvent and the weight ratio of bromine.

In the method for described synthetic alpha-brominated ketone and coproduction hydrobromic ether, to
containing aryl alkyl ketone, the method of dripping bromine is in the mixing liquid of alcohols or epoxy
compounds and water, successively less water and bromine are added dropping funnel, make water
cover the surface of bromine to prevent the volatilization of bromine, in the mixing liquid that contains
ketone compounds and water, drip several bromines then, slowly heating, treat to continue again to drip
after the bromine that originally splashes into fades fully, the bromine that the control temperature of
reaction keeps splashing into fades rapidly, until all dripping, with the water in the dropping funnel
bromine is all washed in the reaction system at last.

In the method for described synthetic alpha-brominated ketone and coproduction hydrobromic ether,
should carry out following selection according to the boiling point of its reactive behavior, product
hydrobromic ether as the alcohols of raw material or the mode in the epoxy compounds adding flask:

1. the reactive behavior junior can add simultaneously with ketone compounds, and active higher can
after the bromo-reaction of ketone is finished, adding;

Or:

2. the boiling point of product hydrobromic ether is higher and when being not suitable for separating
with wet distillation, should be after the ketone bromo-reaction finishes and bromo ketone
crystallization filtering separation is gone out, add alcohols in the mother liquor again or epoxy
compounds reacts, last again with the method separation and purification hydrobromic ether of
distillation.

In the method for described synthetic alpha-brominated ketone and coproduction hydrobromic ether,
the solvent that is used for the alpha-brominated aryl alkyl ketone of washed product is 50～80%
aqueous ethanolic solution.

The technical progress effect that the present invention produces shows with water to be that solvent,
bromine are bromo agent and the synthetic alpha-brominated aryl alkyl ketone compound of multiple
aryl alkyl ketone compound reaction, the hydrogen bromide that produces in reaction formation
Hydrogen bromide soluble in water, again with reaction system in alcohols or the last hydrobromic ether
that generates of epoxy compounds reaction.Make the present invention's coproduction hydrobromic
ether in synthetic brominated ketone compound, improved the utilization ratio of bromine greatly,
avoided the discharging of bromize hydrogen gas and strongly acid wastewater simultaneously.With
traditional technology relatively, have Atom economy height, the energy-saving and emission-reduction
of chemical reaction, the effect of environmental protection.In addition, the present invention as
solvent, has replaced organic solvent with water, has avoided organic solvent pollution on the
environment and harm, is a kind of eco-friendly green synthesis process.
Embodiment

The explanation that following examples are detailed the present invention.

Embodiment 1

The method of a kind of synthetic alpha-brominated methyl phenyl ketone and coproduction
monobromethane, its reaction equation is

Its preparation process is:

In the four-hole boiling flask that agitator, thermometer, dropping funnel and reflux condensing tube are
housed, add 60g (0.5mol) methyl phenyl ketone and 60ml water, add 20ml water in the dropping funnel
earlier, and then adding 80g (0.5mol) bromine, make water cover the surface of bromine, stir and drip
several bromines down, slowly heating, treat to continue to drip remaining bromine again after the
bromine that originally splashes into fades fully, the bromine that the control temperature of reaction
keeps splashing into fades rapidly, all add up to bromine, with the water that is covered in the dropping
funnel above the bromine bromine is all washed in the flask at last.After bromine fades fully, in flask, add
23g (0.5mol) ethanol by dropping funnel again, and change reflux into water distilling apparatus, add
20ml cold water in the receptor in advance, and be placed in the cooling bath and cool off, slowly heat
flask and distill, the monobromethane of generation is constantly steamed, till no oily matter flows out,
stop distillation.

Residuum in the flask is cooled to room temperature, separates out crystal, filtration under diminished
pressure, filtrate is returned the conduct solvent of batch reaction down, and crystal is water and 50%
cold washing with alcohol successively, and drying obtains alpha-brominated methyl phenyl ketone
92.5g, and m.p51 ℃ (lit:51 ℃), productive rate are 93%.

Distillate is left standstill the back branch vibration layer, and organic layer water, 5% yellow soda ash and
water washing successively with distilling after the Calcium Chloride Powder Anhydrous drying, is
collected 38-39 ℃ of cut to neutral, obtains monobromethane 49g, and yield is 90%.

Embodiment 2

A kind of synthetic method to the alpha-brominated methyl phenyl ketone of chloro-and coproduction 1-
n-butyl bromide, its reaction equation is

Its preparation process is:

Agitator is being housed, thermometer, add 75g (0.5mol) parachloroacetophenone in the four-hole
boiling flask of dropping funnel and reflux condensing tube, 37g (0.5mol) 1-butanols, 60ml water and the
1ml vitriol oil, add 20ml water in the dropping funnel earlier, and then adding 80g (0.5mol) bromine,
make water cover the surface of bromine, begin to drip several bromines under stirring, slowly be
heated to backflow, treat to continue to drip remaining bromine again after the bromine that originally
splashes into fades fully, the bromine that the control temperature of reaction keeps splashing into fades
rapidly, all add up to bromine, all wash bromine in the flask with the water that is covered in the funnel
above the bromine at last, after bromine faded fully, heating made steady backflow 2h to reacting
completely.Carry out wet distillation then till do not have oily matter and flow out, stop distillation.

Separate out crystal after residuum in the flask is cooled to room temperature, filtration under
diminished pressure, filtrate can be returned the conduct solvent of batch reaction down, crystal is water
and 50% cold washing with alcohol successively, dry, obtain alpha-brominated parachloroacetophenone
clear crystal 99g, m.p95-96 ℃ (lit:96-96.5 ℃), productive rate is 92%.

Overhead product is left standstill the back branch vibration layer, and water, 5% yellow soda ash and
water washing are to neutral successively again for organic layer, and the Calcium Chloride Powder
Anhydrous drying is distilled at last, collects 100-102 ℃ of cut, obtains 1-n-butyl bromide 65g, and
productive rate is 95%.

Embodiment 3

A kind of synthetic method to methoxyl group-alpha-brominated methyl phenyl ketone and

coproduction 2-n-butyl bromide, its reaction equation is

Its preparation process is:

Agitator is being housed, thermometer, add 75g (0.5mol) p-methoxy-acetophenone in the four-hole
boiling flask of dropping funnel and reflux condensing tube, 37g (0.5mol) 2-butanols and 60ml water,
add 20ml water in the dropping funnel earlier, and then adding 80g (0.5mol) bromine, begin to drip
several bromines under stirring, slowly be heated to 50-60 ℃, treat to continue to drip remaining
bromine again after the bromine that originally splashes into fades fully, the bromine that the control
temperature of reaction keeps splashing into fades rapidly, all add up to bromine, all wash bromine in
the flask with the water that is covered in the funnel above the bromine at last, after bromine fades fully,
slowly heat flask and make steady backflow 1.5h to reacting completely.Carry out wet distillation then till
do not have oily matter and flow out, stop distillation.

Separate out crystal after residuum in the flask is cooled to room temperature, it is overanxious to
reduce pressure, filtrate can be returned down batch reaction as solvent, crystal is water and 50% cold
washing with alcohol successively, dry, obtain alpha-brominated p-methoxy-acetophenone clear crystal
105g, m.p70～71 ℃ (lit:71～72.2 ℃), productive rate is 92%.

Overhead product is left standstill the back branch vibration layer, and water, 5% yellow soda ash and
water washing are to neutral successively for organic layer, and the Calcium Chloride Powder Anhydrous
drying is distilled at last, collects 90-92 ℃ of cut, obtains 2-n-butyl bromide 59g, and productive rate is
86%.

Embodiment 4

A kind of synthetic method to the alpha-brominated methyl phenyl ketone of bromo-and coproduction
bromocyclopentane, its reaction equation is
Its preparation process is:

In the four-hole boiling flask that agitator, thermometer, dropping funnel and reflux condensing tube are
housed, add 99.5g (0.5mol) parabromoacetophenone, 43g (0.5mol) cyclopentanol and 60ml water, add
20ml water in the dropping funnel earlier, and then adding 80g (0.5mol) bromine, begin to drip several
bromines under stirring, slowly heating, treat to continue to drip remaining bromine again after the
bromine that originally splashes into fades fully, the control temperature of reaction is no more than 85
℃, all add up to bromine, after bromine faded fully, slowly heating made steady backflow 1.5h to
reacting completely.Carry out wet distillation then till do not have oily matter and flow out, stop
distillation.

Residuum in the flask is cooled to room temperature, separate out crystal, filtration under diminished
pressure, filtrate can be returned down batch reaction as solvent, crystal is water and 50% cold washing
with alcohol successively, and drying at last must be to the alpha-brominated methyl phenyl ketone clear
crystal of bromo-127g, b.p 109-110 ℃ (lit:110-111 ℃), productive rate 91%.

Overhead product is left standstill the back branch vibration layer, and water, 5% yellow soda ash and
water washing are to neutral successively for organic layer, and the Calcium Chloride Powder Anhydrous
drying is distilled at last, collects 136-139 ℃ of cut, obtains bromocyclopentane 63g, and productive rate
is 85%.

Embodiment 5

A kind of synthetic method to nitro-alpha-brominated methyl phenyl ketone and coproduction ethylene
bromohyrin, its reaction equation is

Its preparation process is:

Agitator is being housed, thermometer, add 82.5g (0.5mol) p-nitroacetophenone and 60ml water in the
four-hole boiling flask of dropping funnel and reflux condensing tube, add 20ml water in the dropping
funnel earlier, and then adding 80g (0.5mol) bromine, begin to drip several bromines under stirring,
slowly be heated to 70 ℃, treat to continue to drip remaining bromine again after the bromine that
originally splashes into fades fully, the control temperature of reaction is no more than 80 ℃, all add up
to bromine, all wash bromine in the flask with the water that is covered in the funnel above the bromine
at last, after bromine faded fully, slowly heating made steady backflow 1.5h to reacting completely, and
stops heating then.Treat to feed when temperature is down to 20 ℃ in the flask 22g (0.5mol) oxyethane,
stirring reaction 1.5h.Distill then, in 99 ℃ of azeotropes that steam ethylene bromohyrin and water.

Residuum is separated out crystal in the flask after being cooled to room temperature, it is overanxious
to reduce pressure, filtrate can be returned the conduct solvent of batch reaction down, crystal is water
and 50% cold washing with alcohol successively, dry, obtain at last nitro-alpha-brominated methyl phenyl
ketone clear crystal 110g, m.p 97-98 ℃ (lit:98 ℃), productive rate 90%.

Extract ethylene bromohyrin with chloroform from azeotrope, extraction liquid distills after with
anhydrous sodium sulfate drying, collects 60-62 ℃ of cut earlier to reclaim chloroform, carries out
underpressure distillation again, collects 52-62 ℃/2.93kPa cut, gets product ethylene bromohyrin 50g,
productive rate 80%.

Embodiment 6

A kind of synthetic to phenyl-alpha-brominated methyl phenyl ketone and coproduction 1, the method
for 3-dibromopropane, its reaction equation is

Its preparation process is:

Agitator is being housed, thermometer, add 98g (0.5mol) p-phenylacetophenone and 60ml water in the
four-hole boiling flask of dropping funnel and reflux condensing tube, add 20ml water in the dropping
funnel earlier, and then adding 80g (0.5mol) bromine, begin to drip several bromines under stirring,
slowly be heated to 70-80 ℃, treat to continue to drip remaining bromine again after the bromine that
originally splashes into fades fully, the control temperature of reaction is no more than 80 ℃, all add up
to bromine, with the water that is covered in the funnel above the bromine bromine is all washed in the
flask at last, after bromine faded fully, slowly heating made steady backflow 3h, stop heating then,
separate out crystal when temperature is down to room temperature in the flask, filtration under
diminished pressure, filtrate is returned in the flask, solid washes with water once, washing lotion is
returned in the flask stand-by with the filtrate merging, and solid is used 50% washing with alcohol
again, must be to phenyl-alpha-brominated methyl phenyl ketone 124g after the drying, m.p137-139 ℃
(lit:138-140 ℃), productive rate 90.3%

In the flask that fills filtrate, add 19g (0.25mol) 1, ammediol and the 1mL vitriol oil, heating reflux
reaction 3h distills then, collects 160-168 ℃ of cut, gets 1,3-dibromopropane 37g, yield 73%.

Embodiment 7

The method of a kind of synthetic β-acetyl bromide naphtho-coproduction 3-bromo-1-propylene, its

reaction equation is

Its preparation process is:

Agitator is being housed, thermometer, add 50g (0.25mol) β-Nai Yitong and 30ml water in the four-hole
boiling flask of dropping funnel and reflux condensing tube, add 10ml water in the dropping funnel
earlier, and then adding 40g (0.25mol) bromine, begin to drip several bromines under stirring, slowly be
heated to 70-80 ℃, treat to continue to drip remaining bromine again after the bromine that originally
splashes into fades fully, the control temperature of reaction is no more than 80 ℃, all add up to
bromine, all wash bromine in the flask with the water that is covered in the funnel above the bromine at
last, after bromine fades fully, slowly heat flask and continue reaction 1h, stop heating then.In flask, add
14g (0.25mol) vinyl carbinol by dropping funnel, stir the sulfuric acid that slowly adds 1ml 98% down
again, continue to be heated to 80 ℃ of reaction 1h.Make reflux into water distilling apparatus and
steam 3-bromo-1-propylene crude product.
Residuum in the flask of distillation back is cooled to room temperature, separates out solid, filters, and
filtrate can be returned the conduct solvent of batch reaction down.Crystal is water and 50% cold
washing with alcohol successively, obtains product β-acetyl bromide naphthalene 66g after the drying,
m.p82-83 ℃ (lit:82-84 ℃), yield 94.6%.

The 3-bromo-1-propylene crude product that steams leaves standstill the back branch vibration layer,
and organic layer is water, 5% yellow soda ash and water washing successively, and the Calcium Chloride
Powder Anhydrous drying is distilled then, collects 69-72 ℃ of cut and obtains 3-bromo-1-propylene,
yield 93%.

Embodiment 8

A kind of synthetic 1-(4-acetylamino phenyl)-2-bromo-1-acetone and coproduction 1, the method for 4-

dibromobutane, its reaction equation is

Its preparation process is:

Agitator is being housed, thermometer, add 95.5g (0.5mol) 1-(4-acetylamino phenyl) acetone and 60ml
water in the four-hole boiling flask of dropping funnel and reflux condensing tube, add 20ml water in the
dropping funnel earlier, and then adding 80g (0.5mol) bromine, begin to drip several bromines under
stirring, slowly be heated to 70-80 ℃, treat to continue to drip remaining bromine again after the
bromine that originally splashes into fades fully, the control temperature of reaction is no more than 65
℃, all add up to bromine, all wash bromine in the flask with the water that is covered in the funnel
above the bromine at last, after bromine fades fully, slowly heat flask and continue reaction 2h, stop
heating then; Reactant is separated out solid after being cooled to room temperature, filters, and filtrate
is returned in the flask, and crystal merges with a small amount of washing, washing lotion and filtrate
again.The solid that leaches obtains 1-(4-acetylamino phenyl)-2-bromo-1-acetone 113.4g, m.p130-131
℃ (lit:129-131 ℃), yield 84% after drying;

In the flask that fills filtrate, add 18g (0.25mol) tetrahydrofuran (THF), and under agitation add the
sulfuric acid of 2ml 98%, continue to be heated to 80-90 ℃ of reaction 4h, cooling, standing demix, tell
crude product, water, 5% sodium carbonate solution and be washed to neutrality successively, after the
Calcium Chloride Powder Anhydrous drying, underpressure distillation, collect 63-65 ℃/700Pa cut,
obtain 1,4-dibromobutane 44g, yield 81%.

Embodiment 9

The method of a kind of synthetic 6-methoxyl group-2-(2-bromine propionyl) naphthalene coproduction

2-methyl-2-N-PROPYLE BROMIDE, its reaction equation is

Its preparation process is:

Agitator is being housed; thermometer; add 107g (0.5mol) 6-methoxyl group-2-propionyl naphthalene
and 60ml water in the four-hole boiling flask of dropping funnel and reflux condensing tube; add 20ml
water in the dropping funnel earlier; and then adding 80g (0.5mol) bromine; begin to drip several
bromines under stirring; slowly be heated to 70-80 ℃; treat to continue to drip remaining bromine again
after the bromine that originally splashes into fades fully; the control temperature of reaction is no more
than 80 ℃; all add up to bromine; all wash bromine in the flask with the water that is covered in the
funnel above the bromine at last; after bromine fades fully, slowly heat flask and continue reaction 1h,
stop heating then.The question response thing adds 18.5g (0.25mol) trimethyl carbinol, stirring reaction
1h under the room temperature by dropping funnel after being chilled to room temperature in
flask.Make reflux into water distilling apparatus and steam 2-methyl-2-N-PROPYLE BROMIDE crude
product.

Residuum in the flask of distillation back is cooled to room temperature; separate out solid; filter; filtrate
can be returned the conduct solvent of batch reaction down; solid is water and 50% washing with
alcohol successively; obtain product 6-methoxyl group-2-(2-bromine propionyl) naphthalene 130.7g after
the drying, m.p:79-81 ℃ (lit:78-80 ℃), yield 94%.

The 2-methyl that steams-2-N-PROPYLE BROMIDE crude product leaves standstill the back and divides
water-yielding stratum, and organic layer is water, 5% yellow soda ash and water washing successively,
and anhydrous sodium sulfate drying distills then, collects 71-74 ℃ of cut, obtains 2-methyl-2-N-
PROPYLE BROMIDE 21g, yield 60%.

Foregoing description only proposes as the enforceable technical scheme of the present invention, not
as the single restricted condition to its technical scheme itself.

Claims (4)

Hide Dependent

1. the method for a synthetic alpha-brominated ketone and coproduction hydrobromic ether, its feature
comprises:

Add aryl alkyl ketone compound in the flask earlier, alcohols or epoxy compounds and water, under
stirring and heating condition, slowly be added drop-wise to bromine in the flask, bromine and ketone
compounds carry out bromo-reaction, generate alpha-brominated ketone and hydrogen bromide, and
the water-soluble formation Hydrogen bromide of hydrogen bromide reacts with alcohols or epoxy
compounds again, generate the brominated hydrocarbons compound, reaction expression is:

Alcohols or the epoxy compounds of the Y representative in the reaction expression, X-Br representative
and product hydrobromic ether thereof;

Carry out wet distillation after reacting completely, the raffinate in the flask of distillation back is alpha-
brominated ketone crude product, separates out crystallization after the cooling, filters, and filtrate is
returned the conduct solvent of batch reaction down; Crystal obtains the alpha-brominated aryl alkyl
ketone of product after washing, drying;

Distillate is the hydrobromic ether crude product, and standing demix divides water-yielding stratum,
and water, 5% yellow soda ash and water washing are to neutral successively for organic layer, and the
Calcium Chloride Powder Anhydrous drying obtains hydrobromic ether through distillation again;

The employed aryl alkyl ketone compound of described synthetic alpha-brominated ketone is selected:

The alpha-brominated aryl alkyl ketone of the product that obtains has following general structure
respectively:

R in the formula be hydrogen atom, (o, m, p)-nitro, 2.4-dinitrobenzene, (o, m, p)-hydroxyl, (o, m, p)-
fluorine, (o, m, p)-chlorine, 2.4-dichloro, (o, m, p)-bromine, (o, m, p)-iodine, (o, m, p)-acetoxyl group, (o,
m, p)-and carboxyl, (o, m, p)-alkoxyl group, (o, m, p)-acetamido, (o, m, p)-and sulfonic group, the p-
phenyl group; R 1Be hydrogen atom, 4 alkyl below the carbon;

The employed alcohols of described coproduction hydrobromic ether or epoxy compounds are selected:

The product hydrobromic ether that obtains has following general structure respectively:

R in the formula be hydrogen atom, (o, m, p)-nitro, 2.4-dinitrobenzene, (o, m, p)-hydroxyl, (o, m, p)-
fluorine, (o, m, p)-chlorine, 2.4-dichloro, (o, m, p)-bromine, (o, m, p)-iodine, (o, m, p)-acetoxyl group, (o,
m, p)-carboxyl, (o, m, p)-alkoxyl group, (o, m, p)-acetamido, (o, m, p)-sulfonic group or p-phenyl; R 1Be
hydrogen atom, 4 alkyl below the carbon; R 2, R 3And R 4Can be hydrogen atom, phenyl or general
molecular formula C nH 2n+1The following alkyl of 13 carbon atoms; R 5And R 6Be hydrogen atom,
general molecular formula C nH 2n+1The following alkyl of 13 carbon atoms; N=1～4 integers.

2. the method for synthetic alpha-brominated ketone according to claim 1 and coproduction
hydrobromic ether, it is characterized in that: aryl alkyl ketone in the described synthetic method, the
mol ratio of bromine and alcohols or epoxy compounds is 1: 1: 1, is 1～1.5: 1 as the water of solvent and
the weight ratio of bromine.

3. the method for synthetic alpha-brominated ketone according to claim 1 and coproduction
hydrobromic ether, it is characterized in that: in the described synthetic method to containing aryl alkyl
ketone, the method of dripping bromine is in the mixing liquid of alcohols or epoxy compounds and
water, successively less water and bromine are added dropping funnel, make water cover the surface of
bromine to prevent the volatilization of bromine, in the mixing liquid that contains ketone compounds
and water, drip several bromines then, slowly heating, treat to continue again to drip after the bromine
that originally splashes into fades fully, the bromine that the control temperature of reaction keeps
splashing into fades rapidly, until all dripping, with the water in the dropping funnel bromine is all
washed in the reaction system at last.

4. the method for synthetic alpha-brominated ketone according to claim 1 and coproduction
hydrobromic ether, it is characterized in that: the solvent that is used for the alpha-brominated aryl alkyl
ketone of washed product in the described method is 50～80% aqueous ethanolic solution.

Patent Citations (1)

Publication number Priority date Publication date Assignee Title

CN101700996A * 2009-09-17 2010-05-05 扬州市天平化工厂有限公司 Method for preparing gamma-

tertiary butyl-chlorobenzene butanone

Family To Family Citations

* Cited by examiner, † Cited by third party

Non-Patent Citations (8)

Title

以水为溶剂合成 α-溴代-邻(对)氯苯乙酮的研究;张书文等;《化学世界》;20090425(第 4 期);第 238-

240 页 *

宫红等.氢溴酸法合成 1-溴代十二烷.《精细化工中间体》.2007,第 37 卷(第 6 期),

对甲氧基-α-溴代苯乙酮的合成研究;王慧敏等;《河南化工》;20040515(第 5 期);第 17-18 页 *

张书文等.以水为溶剂合成 α-溴代-邻(对)氯苯乙酮的研究.《化学世界》.2009,(第 4 期),

彭安顺等.用溴化铜代替液溴合成对甲氧基-溴代苯乙酮.《辽宁化工》.2003,第 32 卷(第 1 期),

氢溴酸法合成 1-溴代十二烷;宫红等;《精细化工中间体》;20071215;第 37 卷(第 6 期);第 45-47 页 *

王慧敏等.对甲氧基-α-溴代苯乙酮的合成研究.《河南化工》.2004,(第 5 期),

用溴化铜代替液溴合成对甲氧基-溴代苯乙酮;彭安顺等;《辽宁化工》;20030228;第 32 卷(第 1 期);

第 17-18 页 *

* Cited by examiner, † Cited by third party

Cited By (3)

Publication number Priority date Publication date Assignee Title

Family To Family Citations

CN102766013A * 2012-06-29 2012-11-07 连云港海水化工有限公司 Environmental-friendly method

for preparing bromine-based alkyl

CN102766014A * 2012-06-29 2012-11-07 连云港海水化工有限公司 Environment friendly method for

preparing bromopropane

CN102875323B * 2012-10-17 2015-07-22 常州大学 Method for preparing bromo-2-methylpropane

through bromination of tertiary butanol in continuous flow micro-channel reactor

* Cited by examiner, † Cited by third party, ‡ Family to family citation

Similar Documents

Publication Publication Date Title

Henne et al. 1947 The Alkaline Condensation of Fluorinated Esters with Esters and Ketones1

JPWO2006001398A1 2008-04-17 Process for producing polyhalogenated diamantane and its derivative

TWI378139B 2012-12-01 A difluorobenzene derivative and a nematic liquid crystal composition using the
same

CN103282344B 2015-02-18 Method for preparation of ketoxime compound and method for preparation
of alkoxy-mine hydrochloride

CN101959840B 2014-04-16 Process for preparing alkyl 2-alkoxymethylene-4,4-difluoro-3-oxobutyrates

CN105263913A 2016-01-20 Thio-1,2,4-triazole derivatives and method for preparing the same

CA2321791A1 1999-09-23 Coupling reactions with palladium catalysts

CN101412670B 2011-11-09 Method for synthesizing loxoprofen sodium

CN102020647B 2013-09-11 Preparation method of 1-(2,2-difluoroethoxy)-6-trifluoromethyl-N-

([1,2,4]triazolezol[1,5-C] pyrimidine-2-)benzsulfamide

CN100391945C 2008-06-04 S-(-)-indolyl-2-carboxylic acid synthesizing method

CN105418460B 2017-04-12 Intermediate of pimavanserin and similar compound thereof, and

preparation method thereof, and method for preparing pimavanserin and similar compound thereof

CN104672157B 2017-06-27 A kind of preparation method of aryltriazolinones

CN104487411A 2015-04-01 Method for producing vinyl esters

WO2009079909A1 2009-07-02 Catalytic reaction-rectification integrated process and specialized device

thereof

CN102276483B 2015-04-15 Production method of oamino pheylmethyl ether

CN101704824B 2011-09-14 Catalytic preparation method of dicyclopentadiene dioxide by quaternary

ammonium heteropoly phosphato tungstate

CN101481378B 2011-07-27 2,3,6,7-tetracarboxylic dianhydride triptycene and method for synthesizing

the same

CN103030719B 2015-12-09 ONS type salicylic alidehyde imine dinuclear metal alkene catalyst and
preparation method

CN101343219B 2012-03-21 Synthesis method of Teprenone

CN102653533A 2012-09-05 Total synthesis method of mangostin

CN103435564A 2013-12-11 Preparation method of tebuconazole

CN101337870B 2011-04-06 Method for synthesizing 4-(4'-n-alkyl cyclohexyl)cyclohexanone

CN106699639A 2017-05-24 Synthesis method of light stabilizer HS-112

CN103539699B 2017-10-27 A kind of synthesis technique of 3,4 difluorobenzonilyiles

CN102276655A 2011-12-14 Dinitrogen heterocyclic carbene dipalladium coordination compound and

preparation method thereof

Priority And Related Applications

Priority Applications (1)

Application Priority date Filing date Title

CN 201010245594 2010-08-05 2010-08-05 Method for synthesizing alpha-bromoketone and

coproducing bromohydrocarbon

Applications Claiming Priority (1)

Application Filing date Title

CN 201010245594 2010-08-05 Method for synthesizing alpha-bromoketone and coproducing

bromohydrocarbon

Legal Events

Date Code Title Description

2011-01-19 PB01 Publication

2011-01-19 C06 Publication

2011-03-16 SE01 Entry into force of request for substantive examination

2011-03-16 C10 Entry into substantive examination

2013-08-14 GR01 Patent grant

2013-08-14 C14 Grant of patent or utility model

2016-09-28 CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130814

Termination date: 20150805

2016-09-28 EXPY Termination of patent right or utility model

Concepts

machine-extracted

Download Filter table

Name Image Sections Count Query match

synthesizing title,abstract,description 3 0.000

water claims,abstract,description 83 0.000

bromine bromine claims,abstract,description 61 0.000

chemical reactions claims,abstract,description 60 0.000

bromine atom bromine atom claims,abstract,description 39 0.000

arylalkyl ketone compounds claims,abstract,description 36 0.000

washing claims,abstract,description 30 0.000

ketones claims,abstract,description 29 0.000

solvents claims,abstract,description 23 0.000

products claims,abstract,description 21 0.000

distillation claims,abstract,description 20 0.000

drying claims,abstract,description 20 0.000

epoxy group claims,abstract,description 17 0.000

heat treatment claims,abstract,description 17 0.000

hydrogen bromide hydrogen bromide claims,abstract,description 17 0.000

polyepoxides claims,abstract,description 17 0.000

stirring claims,abstract,description 13 0.000

crude products claims,abstract,description 11 0.000

organic layers claims,abstract,description 10 0.000

cacl2 cacl2 claims,abstract,description 9 0.000

neutralization claims,abstract,description 7 0.000

cooling claims,abstract,description 5 0.000

Bromoethane Bromoethane claims,description 33 0.000

bromo group bromo group claims,description 25 0.000

alcohols claims,description 15 0.000

filtrates claims,description 15 0.000

hydrogen atoms hydrogen atoms claims,description 12 0.000

hydrogen bromide claims,description 12 0.000

sodium carbonate sodium carbonate claims,description 9 0.000

sodium carbonate claims,description 9 0.000

sodium carbonate claims,description 9 0.000

sodium carbonate claims,description 9 0.000

alkyl group claims,description 8 0.000

calcium chloride claims,description 8 0.000

calcium chloride claims,description 8 0.000

powders claims,description 8 0.000

synthetic method claims,description 7 0.000

liquids claims,description 5 0.000

biosynthetic process claims,description 4 0.000

carbon claims,description 4 0.000

carbon carbon claims,description 4 0.000

carbon atoms carbon atoms claims,description 4 0.000

chlorine claims,description 4 0.000

chlorine claims,description 4 0.000

fluorine claims,description 4 0.000

fluorine claims,description 4 0.000

iodine claims,description 4 0.000

iodine claims,description 4 0.000

mixing claims,description 4 0.000

crystallisation claims,description 3 0.000

formation reactions claims,description 3 0.000

carboxy group carboxy group claims,description 2 0.000

phenyl group phenyl group claims,description 2 0.000

ethanol ethanol abstract,description 12 0.000

layers abstract,description 6 0.000

Ketone Ketone abstract,description 3 0.000

acids abstract,description 3 0.000

effects abstract,description 3 0.000

wastewater abstract,description 3 0.000

atoms abstract,description 2 0.000

discharging abstract,description 2 0.000

substances abstract,description 2 0.000

energy conservation abstract 1 0.000

gases abstract 1 0.000

noxious abstract 1 0.000

steam distillation abstract 1 0.000

Show all concepts from the description section