CN105016942B - The manufacturing method of nitrile and its corresponding amine - Google Patents
The manufacturing method of nitrile and its corresponding amine Download PDFInfo
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- CN105016942B CN105016942B CN201410156038.8A CN201410156038A CN105016942B CN 105016942 B CN105016942 B CN 105016942B CN 201410156038 A CN201410156038 A CN 201410156038A CN 105016942 B CN105016942 B CN 105016942B
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Abstract
The present invention relates to a kind of manufacturing methods of nitrile, compared with prior art, have the characteristics that ammonia source dosage significantly reduces, environmental pressure is small, low energy consumption, production cost is low, the purity and high income of nitrile product, and can obtain the increasingly complex nitrile of structure.The invention further relates to the methods that corresponding amine is manufactured by the nitrile.
Description
Technical field
The method that corresponding amine is manufactured the present invention relates to a kind of manufacturing method of nitrile and by the nitrile.
Background technology
The such as alicyclic dinitrile of alicyclic polynitriles is very important chemical intermediate, it and its derivative are with non-
Normal extensive purposes, for example, the cycloalphatic diamine of one of its derivative just has special property, in dyestuff, medicine, curing
Agent and high molecular polymer etc. extensive application.
The preparation method of alicyclic dinitrile be substantially pass through using existing simple nitrile compounds as raw material it is certain
It reacts to obtain, the substrate spectrum that these methods are applicable in is very narrow, severe reaction conditions, is not suitable for industrialized production.
At this stage, the preparation method of aliphatic polybasic nitrile is mainly using carboxylic acid ammoniation process, but related passes through carboxylic acid ammonification
Method is then rarely reported to manufacture the technology of alicyclic polynitriles.
But the present inventor by the study found that the prior art by aliphatic polycarboxylic acid's ammoniation process come
When manufacturing corresponding aliphatic polybasic nitrile, in order to which aminating reaction is made fully to carry out, which must be in the entire ammonification of carboxylic acid
Into reaction system, persistently supply (being passed through) ammonia source (ammonia) is as raw material in journey or within the longer reaction time, therefore ammonia
Gas dosage is huge, leads to the dosage needed for the actual amount considerably beyond aminating reaction of ammonia, it may be possible to real reaction requirement
Thousands of times, the utilization rate for thus leading to ammonia is extremely low.In addition, the utilization rate due to ammonia is extremely low, which produces
It a large amount of waste ammonia liquor but can not recycle, exert heavy pressures on after discharge to environment, with the environmentally protective life followed now
Production theory is not inconsistent.Moreover, because the aminating reaction of the technology employ overall higher reaction temperature (such as more than 300 DEG C) and
The overall longer reaction time, therefore energy consumption is higher, causes production cost higher, and also deposits reaction mass during the reaction
Loss serious (for example reaction mass being caused to be entrained out reaction system because being continually fed into ammonia flow) and side reaction are more and lead
The quality and yield for causing nitrile product are difficult the problems such as effectively improving.In addition, in order to obtain higher nitrile yield, the prior art will also
The ammonia for using water content extremely low is sought as reaction raw materials, and utilizes the ammonia being continuously passed through during entire aminating reaction
As entrainer, the water of the by-product of discharge reaction at any time.
Therefore, the current present situation of the prior art is to be still required for a kind of manufacturing method of alicyclic polynitriles, preparation side
Method is simple, is suitble to industrialized production.
Invention content
The present inventor by ammoniation process from carboxylic acid to nitrile on the basis of existing technology by diligent the study found that being turned
During change, need the intermediate steps by forming amide, and the intermediate steps only need under relatively low reaction temperature and
It can be completed in the shorter reaction time, and only the intermediate steps just need the supply in ammonia source, thus by the ammoniation process of carboxylic acid
Two independent the step of carrying out clearly are decomposed into, and it has furthermore been found that by using the nitrile system with two particular steps
Make method, it is possible to solve foregoing problems, and have thus completed the present invention.The appearance of this two-step method new process, for breaking
Foreign countries' monopolization, the nitrile compounds and its downstream product for developing China have very important significance.The invention further relates to use
The nitrile manufactures the method for amine.
Specifically, the content the present invention relates to following aspect.
1. a kind of manufacturing method of nitrile, which is characterized in that include the following steps：
First step：Ammonia source without interruption makes carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2ALower contact
0.01-2.5 hours (either 0.05-2 hours either 0.1-1.5 hours either 0.2-1 hours or 0.3-0.8 hours)
Reaction time obtains amide intermediate product, wherein the carboxylic acid sources are selected from alicyclic polycarboxylic acid, the alicyclic polycarboxylic acid
C1-4One or more in linear or branched alkyl group ester and the acid anhydrides of the alicyclic polycarboxylic acid, the ammonia source is with gaseous state
Form is supplied, and T1 is the greater in 145 DEG C of the fusing point that the carboxylic acid sources are depressed in 1 normal atmosphere and temperature value, and T2 is described
Reckling in boiling point, sublimation temperature and decomposition temperature that alicyclic polycarboxylic acid depresses in 1 normal atmosphere, on condition that T2>T1,
It is preferred that T2-T1 >=10 DEG C and second step：Stop supplying the ammonia source, by the amide intermediate product anti-from T3 to T4
Answer temperature TBIt is lower heat treatment 0.1 to 4.5 hour (either 0.2 to 3 hour either 0.3 to 2 hour or 0.4 to 1.2 hour,
Or 0.4 to 1 hour) reaction time, the fusing point and temperature that wherein T3, which is the amide intermediate product, to be depressed in 1 normal atmosphere
The greater in 225 DEG C of value, T4 are boiling point, sublimation temperature and the decomposition temperature that the amide intermediate product is depressed in 1 normal atmosphere
Reckling in degree, on condition that T4>T3, preferably T4-T3 >=10 DEG C.
2. the manufacturing method of the nitrile described in any preceding aspect, wherein the reaction temperature TAFor from T1 ' to T2 ', wherein
T1 '=T1+5 DEG C (or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or
T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C), T2 '=T2 (or T2-5 DEG C or T2-10 DEG C,
Or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C or 310 DEG C), on condition that T2 '>T1′；It is described
Reaction temperature TBFor from T3 ' to T4 ', wherein T3 '=T3+5 DEG C (or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or
T3+40 DEG C or T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C of person), T4 '=T4 (or T4-5
DEG C or T4-10 DEG C or T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C or 350 DEG C), it is preceding
It is T4 ' to carry>T3′.
3. the manufacturing method of the nitrile described in any preceding aspect, wherein T1 for 145 DEG C (either 150 DEG C or 160 DEG C or
170 DEG C of person either 180 DEG C of either 190 DEG C of either 200 DEG C of either 210 DEG C of either 220 DEG C either 230 DEG C or 240
DEG C either 250 DEG C of either 260 DEG C of either 270 DEG C of either 280 DEG C either 290 DEG C or 300 DEG C), T2 for 310 DEG C (or
300 DEG C of person either 290 DEG C of either 280 DEG C of either 270 DEG C of either 260 DEG C of either 250 DEG C either 240 DEG C or 230
DEG C either 220 DEG C of either 210 DEG C of either 200 DEG C either 190 DEG C or 180 DEG C)；T3 for 225 DEG C (or 230 DEG C or
240 DEG C of person either 250 DEG C of either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C or 310
DEG C), T4 for 350 DEG C (either 340 DEG C either 330 DEG C either 320 DEG C either 310 DEG C either 300 DEG C or 290 DEG C or
280 DEG C or 270 DEG C of person).
4. the manufacturing method of the nitrile described in any preceding aspect, wherein the first step in open reactive system into
Row, the second step carry out in open reactive system or closed reaction system.
5. the manufacturing method of the nitrile described in any preceding aspect, wherein catalyst, and institute is not used in the first step
It states second step and carries out or be not used in the presence of a catalyst catalyst.
6. the manufacturing method of the nitrile described in any preceding aspect, wherein the ammonia source is ammonia or the ammonium hydroxide of vaporization, it is excellent
Select the industrial waste ammonia liquor of industrial waste ammonia gas or vaporization, preferably ammonia content 20-99.9wt%, 25-99.9wt%.
7. the manufacturing method of the nitrile described in any preceding aspect, wherein the carboxylic acid sources are carboxylic acid, carboxylic shown in following table
The acid anhydrides or methyl esters of acid, in the first step, reaction temperature TAIt is as shown in the table, the reaction time be 0.05-2 hours or
Person either 0.2-1 hours or 0.3-0.8 hours 0.1-1.5 hours, in the second step, reaction temperature TBSuch as following table
Shown, the reaction time is 0.2 to 3 hour either 0.3 to 2 hour either 0.4 to 1.2 hour or 0.4 to 1 hour.
| Carboxylic acid | Reaction temperature TA, DEG C | Reaction temperature TB, DEG C |
| Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid | 185 to 225 | 245 to 300 |
| 1,2- cyclohexyl dicarboxylic acid | 200 to 265 | 290 to 315 |
| 4- cyclohexene -1,2- dioctyl phthalate | 200 to 265 | 290 to 310 |
| 1,1- ring fourth dioctyl phthalate | 185 to 245 | 270 to 300 |
| 5- norbornene -2,3- dioctyl phthalate | 195 to 240 | 275 to 305 |
| 1,3- adamantane acid | 285 to 300 | 315 to 325 |
| 1,3- ring, penta dioctyl phthalate | 150 to 195 | 235 to 285 |
| 1,2,3,4- ring, penta tetracarboxylic acid | 205 to 260 | 285 to 315 |
| 1,3,5- hexamethylene tricarboxylic acid | 235 to 270 | 300 to 325 |
| 1,2,4,5- hexamethylene tetracarboxylic acid | 180 to 225 | 255 to 300 |
| 1,2,3,4- ring fourth tetracarboxylic acid | 200 to 245 | 275 to 305 |
| 4- methyl -4- cyclohexene -1,2- dioctyl phthalate | 235 to 275 | 300 to 325 |
| 1,3,5,7- adamantane tetracarboxylic acid | 300 to 310 | 325 to 350 |
| Isosorbide-5-Nitrae-cyclohexanedione -2,5- dioctyl phthalate | 155 to 200 | 245 to 295 |
| Isosorbide-5-Nitrae-cyclohexadiene-Isosorbide-5-Nitrae-dioctyl phthalate | 160 to 205 | 255 to 290 |
| 2,2- the third dioctyl phthalate of azacyclo- | 145 to 185 | 225 to 280 |
| 3,3- oxa- ring fourth dioctyl phthalate | 165 to 200 | 250 to 295 |
| 4,5- isoxazole dioctyl phthalate | 170 to 205 | 250 to 300 |
| 2,3- oxygen Polymorphs dioctyl phthalate | 160 to 200 | 235 to 285 |
| Pyrans -2,6- dioctyl phthalate | 155 to 200 | 240 to 290 |
| 1,3-dioxolane -2- methyl -4.5- dioctyl phthalate | 150 to 195 | 245 to 295 |
| 1,3- Pyrimidine -2- methyl -4,5- dioctyl phthalate | 145 to 185 | 235 to 275 |
| 3,4- diamino -2,5- oxygen Polymorphs dioctyl phthalate | 165 to 210 | 240 to 290 |
| 2- methyl -3,4- thiophenedicarboxylic acids | 175 to 225 | 255 to 300 |
| 2,6- thiomorpholine dioctyl phthalate | 145 to 190 | 235 to 280 |
| 3,4- dihydroxy -2,5- oxygen Polymorphs dioctyl phthalate | 145 to 195 | 240 to 305 |
| 4- acetate cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 4- propionyloxy cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 4- caproyl cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 4- lauric acid base cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 2- nitro -4- caproyl cyclohexanecarboxylic acid | 175 to 230 | 245 to 300 |
8. the manufacturing method of the nitrile described in any preceding aspect, wherein the alicyclic polycarboxylic acid, which is selected from, has following knot
It is one or more in the compound of structure formula：
Wherein, groupFor the n valencys C optionally replaced3-20Cycloalkanes hydrocarbon ring, the n valencys C optionally replaced3-20Cycloolefin
Ring or the n valencys C optionally replaced2-20Heterocycle；The divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkane
Ring, the divalent C optionally replaced3-20Cyclenes hydrocarbon ring, the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring is appointed
Choose the divalent C in generation2-20Heterocycle or the divalent combination group optionally replaced, are preferably each independently singly-bound；When n-1 group
The divalent C that B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring, the divalent C optionally replaced3-20Cyclenes hydrocarbon ring is optional
Substituted divalent C2-20During heterocycle, divalent aliphatic hydrocarbon chain that n-1 group R is each independently singly-bound or optionally replaces；Work as n-1
A group B is each independently the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring optionally replaces
When divalent combines group, n-1 group R is each independently the divalent aliphatic hydrocarbon chain optionally replaced；Aliphatic in each definition
Hydrocarbon chain is each independently selected from C1-15(preferably C1-9) saturations or undersaturated straight chain or branch hydrocarbon chain, preferably each independently
Selected from C1-15(preferably C1-9) linear chain or branch chain alkane chain, C2-15(preferably C2-9) linear chain or branch chain alkene chain or C2-15(preferably
C2-9) linear chain or branch chain alkynes chain, more preferably each independently selected from C1-15(preferably C1-9) linear chain or branch chain alkane chain or C2-15
(preferably C2-9) linear chain or branch chain alkene chain；When the carbon atom number of the aliphatic hydrocarbon chain is more than 2 and is included in its strand
During C -- C single bond, insertion-O- ,-S- or-NR optionally between two carbon atoms of the C -- C single bond1-(R1It is H or C1-4Straight chain or branch
Alkyl group)；N is 2 to 10 integer, preferably 2 to 5 integer, more preferable 2 to 4 integer, further preferred 2 or 3.
9. the manufacturing method of the nitrile described in any preceding aspect, wherein the first step produces among the acquisition amide
Effluent containing ammonia is also obtained while object, and described by being used as in the circulation-supplied to the first step of effluent containing ammonia
The supplement or a part in ammonia source, preferably described effluent containing ammonia are being supplied to the first step by concentration or dry Posterior circle
Middle supplement or a part as the ammonia source.
10. a kind of manufacturing method of amine, which is characterized in that include the following steps：
First step：Nitrile is manufactured according to the manufacturing method described in any preceding aspect；With
Second step：The nitrile of first step acquisition is hydrogenated to manufacture amine.
Technique effect
Compared with prior art, the present invention has the following advantages.
Nitrile manufacturing method according to the present invention only supplies ammonia source (such as ammonia etc.) in the first step, and in second step
Stop the supply in ammonia source in rapid completely, therefore the dosage in ammonia source can significantly reduce, and greatly improve the utilization rate in ammonia source.
Nitrile manufacturing method according to the present invention since the utilization rate in ammonia source significantly improves, can be effectively reduced anti-
Waste ammonia liquor amount caused by answering, environmental pressure is small, is consistent with the environmentally protective production theory followed now.
Nitrile manufacturing method according to the present invention does not have strict requirements to the water content in ammonia source, it might even be possible to directly use
Ammonium hydroxide or the ammonium hydroxide of vaporization, it is not required that by the use of the ammonia source as the entrainer of by-product water.Moreover, nitrile system according to the present invention
Method is made, the waste ammonia liquor or useless ammonia (hereafter referred to collectively as effluent containing ammonia) of aminating reaction generation are found that for the first time in this field
It can be introduced directly into the first step of the manufacturing method as the supplement in ammonia source, realize 100% cycle of ammonia-containing water/gas
It utilizes, further reduced the environmental pressure of the manufacturing method.
Nitrile manufacturing method according to the present invention, reaction temperature and reaction time generally significantly drop compared with the prior art
It is low, thus show the advantages of energy consumption reduces, production cost reduces and manufacturing method is simple.
Nitrile manufacturing method according to the present invention, the reaction mechanism mechanism of reaction is simple, and side reaction is less, aminating reaction by impurity effect compared with
Small, thus the manufacturing method is relatively low to the purity requirement in ammonia source and carboxylic acid sources, can directly use respective crude product as anti-
Answer raw material.For example, the present invention has found that the nitrile manufacturing method even can directly use industrial waste containing ammonia for the first time in this field
Or byproduct, as ammonia source, thus the cycle or recycling for various industrial wastes containing ammonia or byproduct open a new way
Diameter meets current environmentally protective production theory.
Nitrile manufacturing method according to the present invention, reaction condition is simple, can be smoothed out (especially even if do not need to catalyst
It is first step), this not only reduces the manufacture cost of nitrile, and also reduces nitrile product later separation or the complexity of purifying
Degree.
Nitrile manufacturing method according to the present invention, first step carry out the shorter reaction time under relatively low reaction temperature,
And stop the supply in ammonia source completely in the second step, therefore the reaction mass caused by ammonia source supply etc. can be substantially reduced and damaged
Lose (entrainment), according to the difference of nitrile product category, the present invention can obtain more than 75%, more than 80%, more than 90%, 95% with
Upper, even more than 98% or higher nitrile yield.
Nitrile manufacturing method according to the present invention, reaction condition is mild, the less generation of side reaction, it is possible thereby to obtain high-purity
Nitrile product (such as more than 97%).
Nitrile manufacturing method according to the present invention, can be produced by carboxylic acid ammoniation process the increasingly complex nitrile of structure (such as
(polynary) nitrile containing various hetero atoms, unsaturated bond or ring structure or (miscellaneous) aromatic series (polynary) nitrile), this is in the art
It is to realize for the first time, so as to be greatly expanded the application range of carboxylic acid ammoniation process.
Amine manufacturing method according to the present invention is raw material due to the use of high-purity nitrile made according to the present invention, therefore
Show the advantages of side reaction is few, product amine purity is corresponding high, production cost is low.
Specific embodiment
The specific embodiment of the present invention is described in detail below, it should be noted however that the protection of the present invention
Range is not limited to these specific embodiments, but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference.
Unless otherwise defined, all technical and scientific terms used herein all has general technology people in fields of the present invention
The equivalent that member understands.In case of conflict, it is interior including being defined on, it is subject to the present specification.
When this specification is come with " well known by persons skilled in the art " or " conventionally known in the art " or similar term
When describing material, method, component, device or equipment, which represents that this specification includes proposing that this field is conventional during the application
Those used, but also include also being of little use at present, but will become art-recognized is suitable for those similar to purpose.
In addition, the various ranges mentioned in this specification is including their endpoint, unless expressly stated otherwise,.This
Outside, when amount, concentration or other values or parameter are provided range, one or more preferred scopes or many preferred upper limit values with it is preferred
During lower limiting value, it should be interpreted as specifically disclosing by arbitrarily to any range upper limit value or preferred value and any range lower limiting value
Or all ranges that preferred value is formed, whether separately disclose these numerical value pair.
In the context of the present specification, unless otherwise defined explicitly or the meaning has exceeded those skilled in the art
Understanding range, more than 3 carbon atoms hydrocarbon or hydrocarbon derivative group (such as propyl, propoxyl group, butyl, butane, butylene, fourth
Alkenyl, hexane when) be respectively provided with when not titled with prefix " just " with titled with prefix " just " when identical meaning.For example, propyl is general
N-propyl is interpreted as, and butyl is generally understood as normal-butyl.
In the context of the present specification, term " ammonia source " refer to can the present invention the nitrile manufacturing method (first step
Suddenly any substance as ammonia sources (providing ammonia) in), the various forms product including ammonia such as liquid ammonia, gaseous ammonia,
Ammonium hydroxide and ammonium hydroxide of vaporization etc., be additionally included under the reaction condition of first step (such as it is anti-by the decomposition such as hydrolyzing or thermally decomposing
Should) substance (hereinafter referred to as producing ammoniacal substance) of ammonia can be generated, for example the ammonium salt of urea, cyanic acid and inorganic acid can be enumerated
(such as ammonium carbonate and ammonium hydrogen carbonate) etc..Nitrile manufacturing method according to the present invention, the reaction mechanism mechanism of reaction is simple, and side reaction is less, ammonification
Reaction is smaller by impurity effect, and thus the manufacturing method is relatively low to the purity requirement in ammonia source.In consideration of it, above and below this specification
Wen Zhong, term " ammonia source " is further included containing ammonia or industrial waste or industry byproduct containing aforementioned production ammoniacal substance, including gaseous state,
The various industrial wastes or industry byproduct of liquid or solid-state form, for example, it is ammonia-containing exhaust (such as from ammonia synthesis process), useless
Ammonia, waste ammonia liquor (such as nitrile manufacturing method from the prior art), useless urea water, useless ammonium bicarbonate water etc..It as long as in general, should
The type or content of impurity in industrial waste or byproduct in addition to ammonia and water do not generate the nitrile manufacturing method of the present invention aobvious
It writes influence (for example the reduction of nitrile yield is made to be no more than 5%) to can be used directly, without carrying out it advance purification process.
This kind of impurity is usually chemically inert for the nitrile manufacturing method of the present invention, for example can enumerate hydrogen, nitrogen, sky
Gas and water steam or liquid water etc. are sometimes considered as the inert diluent of the manufacturing method.Certainly, those skilled in the art pass through
Simple experiment (such as reduction degree by measuring nitrile yield), it will be able to confirm that a certain industrial waste or industry byproduct are
It is no containing or excessively contain the impurity that makes a significant impact of nitrile manufacturing method on the present invention, thereby confirm that whether it can be with
Directly apply to the nitrile manufacturing method of the present invention.In addition, as needed, those skilled in the art can also be by conventionally known
This kind of impurity contained in a certain industrial waste or industry byproduct is reduced to the nitrile for not significantly affecting the present invention by technological means
Manufacturing method implement level and as needed, the concentration of ammonia in a certain industrial waste or industry byproduct is concentrated into more
Suitable for the present invention nitrile manufacturing method implement level (such as by ammonia or produce ammoniacal substance concentration be concentrated into account for the industrial waste or
The 10-95wt% of industry byproduct total amount, preferably 25-95wt%).
In the context of the present specification, term " carboxylic acid sources " refer to can the present invention nitrile manufacturing method (first
Step) middle any substance as carboxylic acid source (providing carboxylic acid), including carboxylic acid starting material in itself and in the anti-of first step
(for example passing through hydrolysis or ammonolysis etc.) can generate the substance (hereinafter referred to as producing carboxylic acid material) of free carboxy acid under the conditions of answering, such as
Carboxylic acid anhydrides and carboxylic acid C can be enumerated1-4Linear or branched alkyl group ester etc..Nitrile manufacturing method according to the present invention, reaction mechanism mechanism of reaction letter
Single, side reaction is less, and aminating reaction is smaller by impurity effect, and thus the manufacturing method is relatively low to the purity requirement of carboxylic acid sources
(for example it can be 90% that purity is minimum), can be directly using industrial corresponding crude product, for example as industry (such as grease
Industry) byproduct (mixing) polybasic carboxylic acid product etc..
In the context of the present invention, term " carboxylic acid " using its it is widest define, refer to containing free carboxy (i.e.-
COOH compound).
In the context of the present specification, term " polybasic carboxylic acid " refer to containing it is multiple (such as 2 to 10, preferably 2 to
5, more preferable 2 to 4, further preferred 2 or 3) compound of free carboxy.
In the context of the present specification, term " aliphatic polycarboxylic acid " refers to each trip with the polybasic carboxylic acid
Carbon atom from carboxyl Direct Bonding is that carbon atom on aliphatic hydrocarbon chain rather than ring are (such as aromatic series or alicyclic
Ring) on carbon atom.
In the context of the present specification, term " alicyclic polycarboxylic acid " is referred at least one with the polybasic carboxylic acid
The carbon atom of free carboxy Direct Bonding is the carbon atom in aliphatic ring (including cycloalkanes hydrocarbon ring, cyclenes hydrocarbon ring and heterocycle), but
Each free carboxy of the polybasic carboxylic acid not with the carbon atom Direct Bonding on aromatic ring (including aromatic ring and hetero-aromatic ring).
In the context of the present specification, term " aromatic polycarboxylic acid " is referred at least one with the polybasic carboxylic acid
The carbon atom of free carboxy Direct Bonding is the carbon atom on aromatic ring (including aromatic ring and hetero-aromatic ring).
In the context of the present specification, term " open reactive system " refers to that the reaction system is outside from beginning to end
Boundary's atmosphere opening (uses open reactive device), and the reaction in the reaction system is in the pressure (ring of (approximation) ambient atmosphere at this time
Border pressure) under carry out.
In the context of the present specification, term " closed reaction system " refer to the reaction system from beginning to end with outside
Boundary's atmospheric isolation (use closed reactor), the reaction in the reaction system at this time the pressure higher than environmental pressure (such as
The self-generated pressure of the reaction system；As long as the safe pressure in production, with regard to there is no particular limitation) under carry out, but not
(such as pressure release or a part of by-product of discharge etc.) as needed is excluded, the reaction system is outwardly big in entire reaction process
The shortness of breath time (for example continuing 0.05-5 minutes, 0.1-4 minutes, 0.3-3 minutes, 0.5-2 minutes or 0.6-1.5 minutes etc.) opens
It puts one or many (such as 1-20 times, 1-10 times, 1-5 times, 1-3 times, 1-2 times or 1 inferior).
In the context of the present specification, term " halogen " refers to fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
In the context of the present specification, statement " optionally replacing " is referred to optionally by one or more (such as 1 to 5
It is a, 1 to 4,1 to 3,1 to 2 or 1) selected from halogen, hydroxyl, sulfydryl, amino, amino carbonyl, nitro, oxo, sulphur
Generation, cyano, C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia,
Carbonyl) base, C2-6Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl, C3-20Cycloalkanes (oxygen, sulphur, ammonia) base,
C3-20Cycloalkyl C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Linear chain or branch chain (halogenated) alkene
(oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group, C3-20
Cyclenes (oxygen, sulphur, ammonia) base, C3-20Cycloalkenyl group C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6
Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia,
Carbonyl) base, C6-20Aryl, C6-20Fragrant (oxygen, sulphur, ammonia) base, C6-20Aryl C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl)
Base, C6-20Aryl C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Linear chain or branch chain (halogenated) alkynes
(oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl, C4-20Heteroaryl (oxygen, sulphur, ammonia) base, C4-20Heteroaryl C1-6Linear chain or branch chain (halogenated)
Alkane (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6
Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle, C2-20Heterocycle (oxygen, sulphur, ammonia) base, C2-20Heterocycle
C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur,
Ammonia, carbonyl) base and C2-20Heterocycle C2-6The substituent group of linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base is (in feasible position
Place) substitution.These substituent groups there are it is multiple when, (such as the molecule last-in-chain(LIC) of two substituent groups between adjacent two substituent groups
End) it can bond together and be formed the substituent structure of divalent.For example, two adjacent C1-6Linear or branched alkyl group can be with that
This is bonded and forms corresponding alkylen structures.Alternatively, two adjacent C1-6Straight or branched alkoxyl can such as form phase
The alkylidene dioxygen based structures answered, adjacent two C1-6Linear chain or branch chain alkylamino can such as form corresponding alkylidene two
Amino structure, adjacent two C1-5Linear chain or branch chain alkylthio group can such as form corresponding alkylidene disulfide group structure, etc.
Deng.As preferred substituent group, for example halogen, hydroxyl, sulfydryl, amino, thio, oxo or C can be enumerated1-6Straight chain or branch
Chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base etc..
In the context of the present specification, statement " (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base " is meant that：It is alkyl, halogenated
Alkyl, alkoxy, alkylthio group, alkylamino, alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, halogenated alkylamino or alkyl halide
Base carbonyl, statement " (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base " are meant that：Alkenyl, halogenated alkenyl, alkenyloxy group, alkenylthio group, alkene ammonia
Base, alkenyl carbonyl, haloalkenyloxy, halogenated alkenylthio group, halogenated enamino or halogenated alkenyl carbonyl state " (halogenated) alkynes
(oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes amino, alkynylcarbonyl groups, acetylenic halide oxygen
Base, acetylenic halide sulfenyl, acetylenic halide amino or halo alkynyl carbonyl, statement " (oxygen, sulphur, ammonia) base " are meant that, oxygroup, sulfenyl
Or amino.Here, it is described it is halogenated including one halogenated, dihalo, three is halogenated or perhalogeno etc..
In the context of the present specification, term " aliphatic hydrocarbon chain " refers to the saturation or unsaturation of straight or branched
Hydrocarbon, including alkane chain, alkene chain and alkynes chain.
In the context of the present specification, term " n valencys " or its structure for referring to being limited from the term similar to term
It is obtained after respectively removing (on a carbon) hydrogen atom on n different carbon atoms in (such as group, hydrocarbon chain or compound ring etc.)
Group.For example, term " divalent " is referred to from the structure (such as group, hydrocarbon chain or compound ring etc.) that the term is limited
2 different carbon atoms on respectively remove the group obtained after (on a carbon) hydrogen atom.Specifically for example, divalent aliphatic hydrocarbon chain
Refer to aliphatic alkylene or aliphatic hydrocarbon diyl.
In the context of the present specification, term " C3-20Cycloalkanes hydrocarbon ring " refers to the list with carbon atom on 3-20 ring
Ring, bicyclic or polycyclic naphthene hydrocarbon ring.As the C3-20Cycloalkanes hydrocarbon ring, for example cyclopropane ring, cyclohexane ring and ring can be enumerated
The monocyclic naphthenes such as pentane ring ring and bicyclic penta ring, decahydronaphthalene naphthalene nucleus, adamantane ring, spiral shell [2.4] heptane ring, spiral shell [4.5] last of the ten Heavenly stems
Alkane ring, two rings [3.2.1] octane ring, tricyclic [2.2.1.02,6] octane ring, norbornane ring,With
It waits loop coils, bridged ring or condensed ring formula is bicyclic or polycyclic naphthene hydrocarbon ring.As the C3-20Cycloalkanes hydrocarbon ring, more preferable C3-15Cycloalkanes hydrocarbon ring.
In the context of the present specification, term " C3-20Cyclenes hydrocarbon ring " refers to aforementioned C3-20Cycloalkanes hydrocarbon ring
Group after carbon-carbon single bond (C-C) is replaced by carbon-carbon double bond (C=C) at least one ring.As the C3-20Cycloolefin
Ring, for example cyclobutane ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, cycloheptyl can be enumerated
The monocyclic cycloalkenyls hydrocarbon rings such as diene ring, cyclo-octatetraene ring and bicyclopentadiene ring, norbornene ring, norbornadiene ring,WithWait loop coils, bridged ring or condensed ring formula bicyclic or polycyclic
Cyclenes hydrocarbon ring.As the C3-20Cyclenes hydrocarbon ring, more preferable C3-15Cyclenes hydrocarbon ring.
In the context of the present specification, term " C6-20Aromatic ring " refers to the aromatic series with carbon atom on 6-20 ring
Hydrocarbon ring.As the C6-20Aromatic ring, for example can to enumerate two or more phenyl ring such as phenyl ring, biphenyl and terphenyl direct with singly-bound
Be connected the group that two or more phenyl ring such as the group formed and naphthalene nucleus, anthracene nucleus, phenanthrene ring condense.As the C6-20
Aromatic ring, more preferable phenyl ring and biphenyl.
In the context of the present specification, term " C4-20Hetero-aromatic ring " is referred to carbon atom and 1-3 on 4-20 ring
Heteroatomic aromatic series hydrocarbon ring on a ring selected from oxygen, sulphur and nitrogen.As the C4-20Hetero-aromatic ring, for example furans can be enumerated
Ring, thiphene ring, pyrrole ring, thiazole ring, benzothiazole ring, Thiadiazole, imidazole ring, benzimidazole ring, triazine ring, triazole ring,
Pyridine ring, pyridine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, pteridine ring and acridine ring etc., wherein it is preferred that furan nucleus, thiophene
Fen ring, imidazole ring, pyridine ring and indole ring etc..
In the context of the present specification, term " C2-20Heterocycle " refers to aforementioned C3-20Cycloalkanes hydrocarbon ring or C3-20Cyclenes
Group after carbon atom is replaced by oxygen atom, sulphur atom or nitrogen-atoms at least one ring of hydrocarbon ring.As the C2-20Heterocycle,
For example piperidine ring, piperazine ring, azepine cyclohexene ring, dioxolane ring, dioxane ring, tetrahydrofuran ring, oxa- can be enumerated
Cyclobutane ring, a word used for translation ring in heptan ring, pyrrolin ring, tetrahydro pyridine ring, tetrahydro-pyrazole ring, pyrazoline ring, pyranoid ring, thiapyran ring, tetrahydrochysene
Pyrrole ring, thiophane ring, aziridine ring, amylene oxide ring, tetrahydric thiapyran ring and morpholine ring etc., wherein it is preferred that piperidine ring, four
Hydrogen furan nucleus, amylene oxide ring etc..
In the context of the present specification, term " combination group " refers to two or more C3-20Cycloalkanes hydrocarbon ring is via list
Group that key or linking group bond together and formed, two or more C3-20Cyclenes hydrocarbon ring via singly-bound or linking group that
This group, two or more C for being bonded and being formed6-20The base that aromatic ring bonds together via singly-bound or linking group and formed
Group, two or more C4-20Group that hetero-aromatic ring bonds together via singly-bound or linking group and formed, two or more C2-20
The group or C that heterocycle bonds together via singly-bound or linking group and formed3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring,
C6-20Aromatic ring, C4-20Hetero-aromatic ring and C2-20In heterocycle it is two or more by condense each other or via singly-bound or linking group that
This group for being bonded and being formed.As the combination group, for example cyclohexyl benzene, tolylthiophene, benzo morpholine, phenyl can be enumerated
Morpholine, cyclohexenyl group pentamethylene, naphthalene norbornane, phenyl adamantane, benzofurane, benzcyclobutane, phenyl pyrazines, phenyl
Pyrroles, cyclohexenyl group adamantane, cyclohexyl oxetanes, cyclohexyl morpholine, Huan hexyls isoxazole, phenyl-isoxazole azoles, Buddha's warrior attendant
Alkane isoxazole, norbornene butylcyclohexane, norbornene benzene, cyclohexyl ring hexane, cyclohexyl methyl hexamethylene, thienyl thiophene
Fen, pyrrole radicals pyrroles, pyrrolidinyl pyrroles, benzyl benzene, phenoxy group benzene, thiophenyl benzene, benzyloxy benzene, benzyloxy methylene
Base benzene, styryl benzene, styryl methylene-benzene, phenyl amino phenyl, phenylaminomethyl benzene, hexamethylene methoxycyclohexyl alkane, benzene methoxy
Base benzene, Deng.
In the context of the present specification, term " linking group " is referred in structure containing there are two be not bonded key (half bond)
Any group, for example can be-O-；-S-；-NR1, wherein R1It is H or C1-4Linear or branched alkyl group, preferably hydrogen or methyl；
The C optionally replaced1-6Linear chain or branch chain alkylene, the C preferably optionally replaced1-4Linear chain or branch chain alkylidene, the C optionally replaced2-4
Linear chain or branch chain alkenylene or the C optionally replaced2-4Linear chain or branch chain alkynylene, the C more preferably optionally replaced1-4Straight chain or branch
Chain alkylidene；Or the arbitrary combination of these linking groups, such as-O-CH2-、-O-CH2-O-、-O-CH2-CH2-CH2-、-O-
CH2-CH2-CH2-S-、-CH2-CH2-CH2-NH-、-CH2-CH2-CH2- S- ,-O-CH=CH-CH2,-O-CH=CH-CH2-O-、-
O-CH2-CH2-CH2-NH-、-O-CH2-O-CH2-CH2-、-O-CH2-O-CH2-CH2-O-、-O-CH2-NH-CH2-CH2- O- etc.,
But-O- ,-S- and-NR1Except situation about being bonded with itself or directly with one another.As the linking group, preferably-O-, optionally
Substituted C1-4Linear chain or branch chain alkylidene or its arbitrary combination, but except the situation of-O- and itself Direct Bonding.
In the context of the present specification, term " effluent containing ammonia " refers to that the manufacturing method in the nitrile of the present invention is (outstanding
It is first step) in reaction carry out during from reaction system as by-product or unreacted raw material discharge contain
The gaseous state or liquid material (such as water containing ammonia condensing, ammonia-containing water and ammonia-containing exhaust etc.) of ammonia.
Finally, in the case where not clearly indicating, all percentages for being previously mentioned in this specification, number, ratio etc.
All it is on the basis of weight, unless on the basis of weight when does not meet the conventional understanding of those skilled in the art.
The present invention relates to a kind of manufacturing methods of nitrile, which is characterized in that including first step and second step as described below
Suddenly.
According to first step, in the case of ammonia source without interruption, make carboxylic acid sources with the ammonia source anti-from T1 to T2
Answer temperature TAIn the reaction time of lower contact 0.01-2.5 hours, amide intermediate product is obtained, wherein, T1 is the carboxylic acid sources 1
The greater in 145 DEG C of the fusing point and temperature value of normal atmosphere pressure, T2 is the alicyclic polycarboxylic acid in 1 standard atmospheric pressure
Under boiling point, the reckling in sublimation temperature and decomposition temperature, on condition that T2>T1.Preferably, T2-T1 >=10 DEG C.
According to the present invention, the carboxylic acid sources are selected from the C of alicyclic polycarboxylic acid, the alicyclic polycarboxylic acid1-4Straight chain or
Branched alkyl ester (preferably methyl esters) or the acid anhydrides of the alicyclic polycarboxylic acid.These carboxylic acid sources can be used alone,
It can also combination of two or more use.
According to the present invention, as the alicyclic polycarboxylic acid, for example the compound such as lower structure can be enumerated.
Wherein, groupFor the n valencys C optionally replaced3-20Cycloalkanes hydrocarbon ring, the n valencys C optionally replaced3-20Cycloolefin
Ring or the n valencys C optionally replaced2-20Heterocycle.
According to the present invention, divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring, optionally
Substituted divalent C3-20Cyclenes hydrocarbon ring, the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring optionally replaces
Divalent C2-20Heterocycle or the divalent combination group optionally replaced, are preferably each independently singly-bound.
According to the present invention, as the divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring is appointed
Choose the divalent C in generation3-20Cyclenes hydrocarbon ring or the divalent C optionally replaced2-20During heterocycle, n-1 group R is each independently singly-bound
Or the divalent aliphatic hydrocarbon chain optionally replaced, and when n-1 group B is each independently the divalent C optionally replaced6-20Aromatic ring is appointed
Choose the divalent C in generation4-20When hetero-aromatic ring or the divalent combination group optionally replaced, n-1 group R, which is each independently, optionally to be taken
The divalent aliphatic hydrocarbon chain in generation.
According to the present invention, the aliphatic hydrocarbon chain in each definition is each independently selected from C1-15(preferably C1-9, such as C1-3)
Saturations or undersaturated straight chain or branch hydrocarbon chain.
, according to the invention it is preferred to the aliphatic hydrocarbon chain in respectively defining is each independently selected from C1-15(preferably C1-9, such as
C1-3) linear chain or branch chain alkane chain, C2-15(preferably C2-9, such as C2-3) linear chain or branch chain alkene chain or C2-15(preferably C2-9, than
Such as C2-3) linear chain or branch chain alkynes chain, more preferably each independently selected from C1-15(preferably C1-9, such as C1-3) linear chain or branch chain alkane
Hydrocarbon chain or C2-15(preferably C2-9, such as C2-3) linear chain or branch chain alkene chain.
According to the present invention, when the carbon atom number of the aliphatic hydrocarbon chain is more than 2 and C -- C single bond is included in its strand
When, a spacer group is optionally further inserted between two carbon atoms of the C -- C single bond：- O- ,-S- or-NR1, wherein R1
It is H or C1-4Linear or branched alkyl group, preferably hydrogen or methyl.The quantity of the C -- C single bond can be one or multiple, than
Such as 1 to 5,1 to 4,1 to 3,1 to 2 or 1.For example, the aliphatic hydrocarbon chain is CH3-CH2-CH2-CH3(in order to
For the sake of facilitating explanation, do not show its valence state) when, it is inserted between the two of a C -- C single bond carbon atoms included in its strand
CH can be obtained after one O3-O-CH2-CH2-CH3、CH3-CH2-O-CH2-CH3And CH3-CH2-CH2-O-CH3Deng in two C-C
CH can be obtained after being inserted into an O respectively between respective two carbon atoms of singly-bound3-O-CH2-O-CH2-CH3、CH3-CH2-O-
CH2-O-CH3And CH3-O-CH2-CH2-O-CH3Deng being inserted into an O respectively between respective two carbon atoms of three C -- C single bonds
After can obtain CH3-O-CH2-O-CH2-O-CH3。
According to the present invention, n is 2 to 10 integer, preferably 2 to 5 integer, more preferable 2 to 4 integer, further preferred 2
Or 3.
According to the present invention, aliphatic hydrocarbon chain described here, C3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring, C6-20Aromatic ring,
C4-20Hetero-aromatic ring, C2-20Heterocycle and combination group are defined as previously described.
According to the present invention, as the carboxylic acid sources, aforementioned alicyclic polycarboxylic acid can be used alone, can also
Combination of two or more uses.
According to the present invention, the carboxylic acid sources can be biological source, for example, can enumerate natural polybasic carboxylic acid or
(mixing) polybasic carboxylic acid product as industrial (such as oil prodution industry) byproduct etc., as long as impurity or water impurity contained by it
The flat reduction for making target nitrile yield is no more than 5%.
According to the present invention, the carboxylic acid sources are in the reaction temperature TAUnder be preferably presented as molten condition or liquid
State.In consideration of it, the alicyclic polycarboxylic acid, the C of the alicyclic polycarboxylic acid1-4Linear or branched alkyl group ester is described
The acid anhydrides of alicyclic polycarboxylic acid, which preferably has, is equal to or less than the reaction temperature TAThe fusing point (1 of (being typically up to 310 DEG C)
Normal atmosphere pressure measures).Those skilled in the art can be by consulting the relevant technologies handbook or passing through conventional determining method
Know (and the boiling that the alicyclic polycarboxylic acid depresses in 1 normal atmosphere of fusing point that these carboxylic acid sources depress in 1 normal atmosphere
Point, sublimation temperature and decomposition temperature etc.), therefore repeat no more herein.
According to the present invention, as the mode that carboxylic acid sources is made to be contacted with ammonia source, for example can enumerate to melting in advance
The mode in the ammonia source of gaseous form is continuously passed through in carboxylic acid sources.
According to the present invention, the ammonia source is as it was noted above, wherein preferred ammonia or the ammonium hydroxide of vaporization, particularly Industry Waste
Ammonia or the industrial waste ammonia liquor of vaporization.The ammonia content in the ammonia source such as can be 20-99.9wt%, 25- at this time
99.9wt%, 40-99.9wt%, 60-99.9wt%, 75-99.9wt%, 85-99.9wt% or 95-99.9wt%, remaining
It is then previously described inert diluent etc..
According to the present invention, (being passed through) without interruption during the entire process of the first step described ammonia source.As at this time
(totality) dosage in the ammonia source as long as the scheduled nitrile yield of the present invention can be realized, is not particularly limited.Such as
According to real reaction situation, carboxylic acid sources in terms of carboxyl with NH3The minimum molar ratio in the ammonia source of meter can be 1:
20th, 1: 30,1: 40 or 1: 50 etc., highest is subject to the excess waste for not leading to ammonia source, for example can be 1: 500,1: 400,1
: 300,1: 200,1: 100 or 1: 80 etc., but is not limited thereto.
According to the present invention, the first step carries out in open reactive system (such as open reactive kettle).Ammonia source
While the reaction system (carboxylic acid sources containing melting) are continuously supplied to, effluent containing ammonia is continuously vented the reaction
System., it is preferred according to the present invention that by (after the concentration or drying) circulation-supplied of effluent containing ammonia described in
Supplement or a part in first step as the ammonia source.It so can accordingly reduce supplied to the fresh of the first step
Thus the dosage in ammonia source improves the utilization rate of ammonia raw material, and realizes effluent containing ammonia (such as ammonia-containing water and ammonia-containing exhaust)
Efficient Cycle utilizes.
It was found by the inventors of the present invention that it can be carried out well the first step is even if without using catalyst.Therefore,
According to a preferred embodiment of the present invention, the first step usually makes without using when carrying out carboxylic acid ammoniation process in this field
Any catalyst.
According to the present invention, reaction time of the first step be preferably 0.05-2 hours or 0.1-1.5 hours or
Person 0.2-1 hours either 0.3-0.8 hours or the shorter time.
According to the present invention, after the first step, stop the supply in the ammonia source immediately.
According to the present invention, after the first step, the amide intermediate product that is obtained can directly as raw material into
Row second step can also carry out second step again after temporary wait.Although alternatively, not necessarily, among the amide obtained
Product can also be washed using weak aqua ammonia etc., to remove possible remaining unreacted carboxylic acid sources.
According to the present invention, the first step and second step can carry out in same reaction vessel, can also be
It carries out, is not particularly limited in different reaction vessels (such as tandem reaction vessel).In same reaction vessel
During progress, after the first step, do not discharge the amide intermediate product, and the reaction condition of first step is directly changed
Become the reaction condition (as described below) of second step, production cost and the production for thus reducing the manufacturing method are complicated
Degree.
According to the second step, the amide intermediate product that first step is obtained is in the reaction temperature from T3 to T4
TBThe reaction time of lower heat treatment 0.1 to 4.5 hour, wherein T3 are that the amide intermediate product is melted what 1 normal atmosphere was depressed
Point and 225 DEG C of temperature value in the greater, T4 be the amide intermediate product depressed in 1 normal atmosphere boiling point, sublimation temperature
With the reckling in decomposition temperature, on condition that T4>T3.Preferably, T4-T3 >=10 DEG C.
According to the present invention, the amide intermediate product is in the reaction temperature TBUnder be preferably presented as molten condition or liquid
Body state.In consideration of it, the amide intermediate product, which preferably has, is equal to or less than the reaction temperature TB(it is typically up to 350
DEG C) fusing point (1 normal atmosphere pressure measure).Those skilled in the art can be by consulting the relevant technologies handbook or by normal
Rule assay method knows fusing point, boiling point, sublimation temperature and decomposition temperature that these amide intermediate products are depressed in 1 normal atmosphere
Deng, therefore repeat no more herein.
According to the present invention, preferably 0.2 to 3 hour reaction time of the second step either 0.3 to 2 hour or
0.4 to 1.2 hour either 0.4 to 1 hour or shorter time.
According to the present invention, stop the supply in the ammonia source completely in the second step.
According to the present invention, the second step can also be in closed reaction system in open reactive system
It carries out, is preferably carried out in closed reaction system, to reduce energy consumption.
According to the present invention, the second step can carry out in the presence of a catalyst, can not also use catalyst.Make
For the catalyst, for example those conventional use of catalyst when carboxylic acid ammoniation process is carried out in this field can be enumerated, such as five
Two phosphorus, phosphoric acid, phosphate, molecular sieve, aluminium oxide, zinc oxide or composite oxide catalysts etc. are aoxidized, wherein it is preferable to use
Phosphorus pentoxide or phosphoric acid.When in use, these catalyst can be according to the conventional amount used of this field (such as on the basis of weight
Can be the 0.2-10% of the carboxylic acid sources weight, preferably 1-6%) it uses, it is not particularly limited.
According to a further embodiment of the invention, the reaction temperature TAFor from T1 ' to T2 '.It is at this point, described
T1 '=T1+5 DEG C or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or
T1+60 DEG C or T1+70 DEG C or T1+80 DEG C or T1+90 DEG C.The T2 '=T2 or T2-5 DEG C or T2-10
DEG C or T2-20 DEG C or T2-30 DEG C or T2-40 DEG C or T2-50 DEG C, but typically up to for 310 DEG C, on condition that
T2′>T1′.Preferably, T2 '-T1 ' >=10 DEG C.
According to a further embodiment of the invention, the reaction temperature TBFor from T3 ' to T4 '.It is at this point, described
T3 '=T3+5 DEG C or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or T3+50 DEG C or
T3+60 DEG C or T3+70 DEG C or T3+80 DEG C.The T4 '=T4 or T4-5 DEG C or T4-10 DEG C or T4-20
DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C, but typically up to be 350 DEG C.On condition that T4 '>T3′.Preferably
It is T4 '-T3 ' >=10 DEG C.
According to a further embodiment of the invention, the T1 for 145 DEG C either 150 DEG C or 160 DEG C or
170 DEG C of person either 180 DEG C of either 190 DEG C of either 200 DEG C of either 210 DEG C of either 220 DEG C either 230 DEG C or 240
DEG C either 250 DEG C of either 260 DEG C of either 270 DEG C of either 280 DEG C either 290 DEG C or 300 DEG C.According to one of the invention
Further embodiment, the T2 for 310 DEG C either 300 DEG C either 290 DEG C either 280 DEG C either 270 DEG C or
260 DEG C of either 250 DEG C of either 240 DEG C of either 230 DEG C of either 220 DEG C of either 210 DEG C either 200 DEG C or 190 DEG C,
Or 180 DEG C.On condition that T2>T1.Preferably, T2-T1 >=10 DEG C.
According to a further embodiment of the invention, the T3 for 225 DEG C either 230 DEG C or 240 DEG C or
250 DEG C of person either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C or 310 DEG C.According to this hair
A bright further embodiment, the T4 are 350 DEG C of either 340 DEG C of either 330 DEG C either 320 DEG C or 310
DEG C either 300 DEG C of either 290 DEG C either 280 DEG C or 270 DEG C.On condition that T4>T3.Preferably, T4-T3 >=10 DEG C.
According to a specific embodiment of the invention, the carboxylic acid sources are the acid of carboxylic acid shown in the following table 1, the carboxylic acid
Acid anhydride or methyl esters (preferably described carboxylic acid), in the first step, reaction temperature TAAs shown in table 1 below, the reaction time is 0.05-
2 hours either 0.1-1.5 hours either 0.2-1 hours or 0.3-0.8 hours, in the second step, reaction temperature
TBAs shown in table 1 below, the reaction time is 0.2 to 3 hour either 0.3 to 2 hour either 0.4 to 1.2 hour or 0.4 to 1
Hour.
Table 1
| Carboxylic acid | Reaction temperature TA, DEG C | Reaction temperature TB, DEG C |
| Isosorbide-5-Nitrae-cyclohexyl dicarboxylic acid | 185 to 225 | 245 to 300 |
| 1,2- cyclohexyl dicarboxylic acid | 200 to 265 | 290 to 315 |
| 4- cyclohexene -1,2- dioctyl phthalate | 200 to 265 | 290 to 310 |
| 1,1- ring fourth dioctyl phthalate | 185 to 245 | 270 to 300 |
| 5- norbornene -2,3- dioctyl phthalate | 195 to 240 | 275 to 305 |
| 1,3- adamantane acid | 285 to 300 | 315 to 325 |
| 1,3- ring, penta dioctyl phthalate | 150 to 195 | 235 to 285 |
| 1,2,3,4- ring, penta tetracarboxylic acid | 205 to 260 | 285 to 315 |
| 1,3,5- hexamethylene tricarboxylic acid | 235 to 270 | 300 to 325 |
| 1,2,4,5- hexamethylene tetracarboxylic acid | 180 to 225 | 255 to 300 |
| 1,2,3,4- ring fourth tetracarboxylic acid | 200 to 245 | 275 to 305 |
| 4- methyl -4- cyclohexene -1,2- dioctyl phthalate | 235 to 275 | 300 to 325 |
| 1,3,5,7- adamantane tetracarboxylic acid | 300 to 310 | 325 to 350 |
| Isosorbide-5-Nitrae-cyclohexanedione -2,5- dioctyl phthalate | 155 to 200 | 245 to 295 |
| Isosorbide-5-Nitrae-cyclohexadiene-Isosorbide-5-Nitrae-dioctyl phthalate | 160 to 205 | 255 to 290 |
| 2,2- the third dioctyl phthalate of azacyclo- | 145 to 185 | 225 to 280 |
| 3,3- oxa- ring fourth dioctyl phthalate | 165 to 200 | 250 to 295 |
| 4,5- isoxazole dioctyl phthalate | 170 to 205 | 250 to 300 |
| 2,3- oxygen Polymorphs dioctyl phthalate | 160 to 200 | 235 to 285 |
| Pyrans -2,6- dioctyl phthalate | 155 to 200 | 240 to 290 |
| 1,3-dioxolane -2- methyl -4.5- dioctyl phthalate | 150 to 195 | 245 to 295 |
| 1,3- Pyrimidine -2- methyl -4,5- dioctyl phthalate | 145 to 185 | 235 to 275 |
| 3,4- diamino -2,5- oxygen Polymorphs dioctyl phthalate | 165 to 210 | 240 to 290 |
| 2- methyl -3,4- thiophenedicarboxylic acids | 175 to 225 | 255 to 300 |
| 2,6- thiomorpholine dioctyl phthalate | 145 to 190 | 235 to 280 |
| 3,4- dihydroxy -2,5- oxygen Polymorphs dioctyl phthalate | 145 to 195 | 240 to 305 |
| 4- acetate cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 4- propionyloxy cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 4- caproyl cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 4- lauric acid base cyclohexanecarboxylic acid | 185 to 225 | 245 to 300 |
| 2- nitro -4- caproyl cyclohexanecarboxylic acid | 175 to 230 | 245 to 300 |
According to the present invention, after the second step, by conventional purification or separation methods, you can from second step
Suddenly target nitrile is isolated in the reaction mixture obtained as product.As the purifying or separation method, for example can enumerate
The way of distillation and extraction etc..
According to the present invention, the way of distillation or extraction can carry out in a manner that this field is conventional, and there is no especially
Restriction, as long as target nitrile product can be separated from the reaction mixture.
According to the present invention, as the way of distillation, for example the distillation under vacuum for having used rectifying column can be enumerated, the rectifying
The operating condition of tower at this time is such as：Vacuum degree is 25-250mbar, and column bottom temperature is generally 100-320 DEG C, is produced with target nitrile
Boiling point (± 2 DEG C) of the product under the vacuum degree is such as generally 80-290 DEG C, but it is not limited to this but takes as cut point
Certainly in specific target nitrile product.As needed, the reflux ratio of the rectifying column can be set as the 1.1-4 of minimum reflux ratio Rmin
Times, number of actual plates is such as 5-200 blocks, and but it is not limited to this but depends on specific target nitrile product.In addition, the essence
The practical operation condition for evaporating tower is not limited to this, those skilled in the art can according to the distillation character of target nitrile product (such as
Boiling point and heat decomposition temperature etc.), rectifying tower structure (such as plate number etc.) and actual needs (such as scheduled nitrile purity etc.)
The distillation operation condition for waiting selections appropriate, this is all conventionally known.
According to the present invention, as the extraction, for example can enumerate using the targets nitrile such as ethyl acetate, chloroform, hexane
The good solvent of product to the reaction mixture (as needed add in suitable 2-5wt% dilute alkaline aqueous solutions be diluted or
After adjusting) method that is directly extracted etc..
According to the present invention, extraction and the way of distillation can be combined, for example preliminary purifying can be carried out first with extraction
Or separation, then further purified or detached by the way of distillation.
According to the present invention, by the purifying or separation, can obtain purity for more than 97% (preferably more than 98%, more
It is preferred that more than 99%) target nitrile product.Nitrile purity at this time such as can be easily measured by gas chromatography etc..
Nitrile manufacturing method according to the present invention, according to the difference of nitrile product category, can realize more than 75%, 80% with
Upper, more than 90%, more than 95%, even more than 98% or higher nitrile yield.
According to the present invention, the nitrile can be used as raw material for manufacturing corresponding amine.For this purpose, the invention further relates to a kind of amine
Manufacturing method, which manufactures corresponding amine by hydrogenating the nitrile.
According to the present invention, the hydrogenation can in hydrogenated nitrile, any mode carries out known to routine according to this field.Than
Such as, can be 0.6-5.2MPa in reaction gross pressure, hydrogen partial pressure is 0.4-5MPa (such as 2-4MPa), reaction temperature 70-
Under conditions of 130 DEG C (such as 80-120 DEG C), in the presence of a hydrogenation catalyst, make the nitrile raw material hydrogenate 0.2-3 hours it is (excellent
Select 0.5-2 hours), but is not limited thereto.
It, can be directly using this field conventionally used for hydrogenating nitriles amine as the hydrogenation catalyst according to the present invention
Various catalyst, for example the Raney's nickel of the doping such as Raney's nickel, iron or copper can be enumerated, Ni-B or Ni-Co-B amorphous alloys, born
Load type Ni-B or Ni-Co-B amorphous alloy, carrier loaded noble metal (such as Pb/C, Pd/C or Rh/C etc.) compound are urged
Agent (such as Raney's nickel/eight carbonyl cobalt) etc., wherein facilitating the angle of implementation, preferably Raney's nickel, such as Aladdin from industrialization
50 μm or 150 μm commercially available Raney's nickels of specification are pressed by Reagent Company.These hydrogenation catalysts can be used alone, can also two kinds or
Multiple combinations use.
According to the present invention, the dosage of the hydrogenation catalyst such as can be the 2- of the nitrile raw material on the basis of weight
10wt% (such as 2-6wt%), but is not limited thereto.
According to the present invention, the hydrogenation preferably carries out in the presence of solvent (or being diluent), this is ability
Known to domain.As the solvent, for example water can be enumerated；The alcohol such as methanol, ethyl alcohol and 2- propyl alcohol；The esters such as methyl acetate；Benzene, first
The aromatic hydrocarbon such as benzene, dimethylbenzene；The cycloalkane such as hexamethylene；The alkane such as heptane；Petroleum ether, ether, dioxane and tetrahydrofuran etc.
The arbitrary combination wherein mixed solvent of the preferred alcohol or ethyl alcohol and water (volume ratio of ethyl alcohol and water of ether either these solvents
For example be 0.1: 1 to 1: 0.1, but it is not limited to this) etc..These solvents can be used alone, can also combination of two or more
It uses.
According to the present invention, as the dosage of the solvent, as long as the heat release situation of reaction and not can be effectively improved
Excessive burden is generated to subsequent product separating step, for example on the basis of volume can be the 1-10 of the nitrile raw material
Times, such as 1-5 times, 1-4 times, 1-3 times or 1-2 times etc., but is not limited thereto.
According to the present invention, as needed, the hydrogenation can also carry out in the presence of auxiliary agent is hydrogenated.As described
Auxiliary agent is hydrogenated, for example the alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide can be enumerated.These hydrogenation auxiliary agents
It can be used alone, it can also combination of two or more use.
Can be the nitrile raw material as the dosage of the hydrogenation auxiliary agent, such as on the basis of weight according to the present invention
0.3-2wt% (preferably 0.2-1.2wt%), but is not limited thereto.
According to the present invention, after the hydrogenation, by conventional purification or separation methods, you can mixed from reaction
It closes in object and isolates targeted amine as product.These purifying or separation method are known in the art, and details are not described herein.
The manufacturing method of amine according to the present invention, according to the difference of nitrile raw material type, can realize more than 85%, 90% with
Upper, more than 95%, even more than 98% or higher amine yield, and the purity of amine product can reach more than 97% (preferably
More than 98%, more preferable more than 99%).
Embodiment
The present invention is illustrated using embodiment in further detail below, but the present invention is not limited to these embodiments.
Amide intermediate prepares embodiment
It is open in reaction kettle in 1L and adds in 500g carboxylic acid starting materials (chemistry is pure), stirring (600r/min) is opened, from reaction kettle
Bottom is constantly passed through ammonia (chemistry pure, water content 5.1wt%, flow 100g/min) into carboxylic acid starting material.Reaction is made to exist
Reaction temperature TALower carry out TCAfter hour, stopping is passed through ammonia.The content of reaction kettle is sampled, does nucleus magnetic hydrogen spectrum and element point
Analysis, to characterize amide intermediate.Specific reaction condition and characterization result are shown in following Table A -1, Table A -2, Table A -3, Table A -4 and table
A-5.These characterization results show that obtained amide intermediate has high purity (more than 99%).
Table A -1
Table A -2
Table A -3
Table A -4
Table A -5
Nitrile product prepares embodiment
The amide intermediate that continues prepares embodiment.The reaction kettle is closed (when the boiling point of amide intermediate under normal pressure etc.
In or less than following reaction temperature TBWhen) or keep reaction kettle for open state (when the boiling of amide intermediate under normal pressure
Point is higher than following reaction temperature TBWhen), continue to stir (600r/min), reaction temperature is changed into TB, in reaction temperature TB
Lower holding TDAfter hour, capping kettle simultaneously connects vacuum pump, and the vacuum degree in reaction kettle is made to reach 20-50mbar (according to nitrile
The difference of product species and accordingly adjust), using distillate as nitrile product.The yield of the nitrile product is calculated, and samples and does nuclear-magnetism
Hydrogen is composed and elemental analysis, to characterize obtained nitrile product.Specific reaction condition and characterization result see following Table A -6, A-7,
A-8, A-9 and A-10.These characterization results show that obtained nitrile product has high purity (more than 99%).
These nitrile products prepare embodiment in, optionally reaction start stage, 10g is disposably added in into reaction kettle
Phosphorus pentoxide is as catalyst.
Table A -6
Table A -7
Table A -8
Table A -9
Table A -10
Amine prepares embodiment
(1) 100g1,4- hexamethylenes dimethoxy nitrile and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, is continuously filled with
H2, system pressure in reaction process is made to be always maintained at 5MPa.At 95 DEG C of reaction temperature after reaction 0.5h, cooling.It waits to react
When temperature in kettle is down to room temperature, deflate, by filtering and being recrystallized to give Isosorbide-5-Nitrae-hexamethylene dimethylamine (purity is more than 99%),
Yield is 90wt%.
1H NMR (300MHz, DMSO) δ 2.54-2.50 (m, 2H), 2.49 (d, J=2.2Hz, 2H), 1.94 (s, 4H),
1.89-1.78 (m, 4H), 1.20-0.87 (m, 6H), E1emental Analysis：C, 67.18；H, 12.16；N, 19.28.
(2) 100g4- cyclohexene -1,2- dimethoxy nitrile and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, even
It is continuous to be filled with H2, system pressure in reaction process is made to be always maintained at 6MPa.At 90 DEG C of reaction temperature after reaction 1h, cooling.It treats
It when temperature in reaction kettle is down to room temperature, deflates, by filtering and being recrystallized to give 4- cyclohexene -1,2- dimethylamine, (purity is
More than 99%), yield 91wt%.
1H NMR (300MHz, DMSO) δ 5.69 (d, J=11.0Hz, 1H), 5.74-5.56 (m, 2H), 5.64 (d, J=
4.5Hz, 1H), 2.77-2.59 (m, 2H), 3.41-2.58 (m, 2H), 2.53-2.42 (m, 2H), 2.55-2.32 (m, 4H),
2.42-2.32 (m, 2H), 2.07 (ddd, J=12.4,8.3,7.0Hz, 2H), 2.07 (ddd, J=12.4,8.3,7.0Hz,
2H), 1.95 (s, 4H), 1.95 (s, 4H), 1.63-1.50 (m, 1H), 1.62-1.37 (m, 2H), 1.50-1.39 (m, 1H),
Elemental Analysis：C, 68.17；H, 11.05；N, 19.24.
(3) 100g1,3,5- hexamethylene trimethylsilyl nitriles and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, is continuously filled
Enter H2, system pressure in reaction process is made to be always maintained at 6MPa.At 100 DEG C of reaction temperature after reaction 1h, cooling.It waits to react
When temperature in kettle is down to room temperature, deflate, by filter and be recrystallized to give 1,3,5- hexamethylene trimethylamines (purity for 99% with
On), yield 89wt%.
1H NMR (300MHz, DMSO) δ 2.50 (d, J=7.2Hz, 6H), 1.97-1.90 (m, 8H), 1.88 (s, 1H),
1.26-1.18 (m, 1H), 1.16 (s, 1H), 1.15-1.06 (m, 1H), 0.72 (d, J=7.7Hz, 2H), 0.68 (s, 1H),
E1emental Analysis：C, 63.01；H, 12.14；N, 24.19.
(4) 100g2,3- oxygen Polymorphs dimethoxy nitriles and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, continuously
It is filled with H2, system pressure in reaction process is made to be always maintained at 6MPa.At 85 DEG C of reaction temperature after reaction 1h, cooling.It treats anti-
When answering the temperature in kettle to be down to room temperature, deflate, by filtering and being recrystallized to give 2,3- oxygen Polymorphs dimethylamine (purity 99%
More than), yield 91wt%.
1H NMR (300MHz, DMSO) δ 3.99 (dt, J=9.0,7.3Hz, 1H), 3.89-3.67 (m, 2H), 2.88 (dd,
J=12.4,7.3Hz, 1H), 2.66 (ddd, J=19.4,12.4,7.1Hz, 2H), 2.44 (dd, J=12.4,7.0Hz, 1H),
2.15 (s, 2H), 2.08 (s, 2H), 1.91 (ddd, J=13.7,11.7,6.7Hz, 1H), 1.85-1.73 (m, 1H), 1.73-
1.55 (m, 1H), Elemental Analysis：C, 55.17；H, 10.52；N, 21.43.
(5) 100g1,2,3,4- ring fourth, four formonitrile HCN and 3g Raney-Ni, 400mL ethyl alcohol are added in 1L adds hydrogen kettle, continuously
It is filled with H2, system pressure in reaction process is made to be always maintained at 8MPa.At 95 DEG C of reaction temperature after reaction 1h, cooling.It treats anti-
When answering the temperature in kettle to be down to room temperature, deflate, by filtering and being recrystallized to give 1,2,3,4- ring fourth tetramethylammonium (purity 99%
More than), yield 88wt%.
1H NMR (300MHz, DMSO) δ 2.55-2.46 (m, 8H), 2.24 (s, 8H), 1.80-1.63 (m, 4H),
Elemental Analysis：C, 55.18；H, 11.17；N, 32.26.
Although the specific embodiment of the present invention is described in detail above in conjunction with the embodiments, need to refer to
Go out, the scope of protection of the present invention is not limited by these specific embodiments, but by claims of annex Lai
It determines.Those skilled in the art can carry out these embodiments in the range of the technological thought of the present invention and purport is not departed from
Appropriate change, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (37)
1. a kind of manufacturing method of nitrile, which is characterized in that include the following steps：
First step：Ammonia source without interruption makes carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2ALower contact 0.01-
The reaction time of 2.5 hours obtains amide intermediate product, wherein the carboxylic acid sources are selected from alicyclic polycarboxylic acid, the alicyclic ring
The C of race's polybasic carboxylic acid1-4It is one or more in linear or branched alkyl group ester and the acid anhydrides of the alicyclic polycarboxylic acid, it is described
Ammonia source is supplied in a gaseous form, and T1 is larger in 145 DEG C of the fusing point that the carboxylic acid sources are depressed in 1 normal atmosphere and temperature value
Person, T2 are the recklings in boiling point, sublimation temperature and the decomposition temperature that the alicyclic polycarboxylic acid depresses in 1 normal atmosphere,
On condition that T2 ＞ T1,
With
Second step：Stop supplying the ammonia source, by the amide intermediate product in the reaction temperature T from T3 to T4BLower heat treatment
The reaction time of 0.1 to 4.5 hour, wherein T3 are the fusing point and temperature value that the amide intermediate product is depressed in 1 normal atmosphere
The greater in 225 DEG C, T4 are boiling point, sublimation temperature and the decomposition temperature that the amide intermediate product is depressed in 1 normal atmosphere
In reckling, on condition that T4 ＞ T3,
The first step carries out in open reactive system,
The ammonia source is ammonia, and the ammonia content in the ammonia source is 75-95wt%, remaining is inert diluent, the inert diluents
Agent is selected from vapor or liquid water,
The alicyclic polycarboxylic acid refers to that the carbon atom at least one free carboxy Direct Bonding of the polybasic carboxylic acid is
Carbon atom in aliphatic ring, but each free carboxy of the polybasic carboxylic acid not with the carbon atom direct key on aromatic ring
It closes, and one or more in the compound of formula selected from having the following structure：
Wherein, groupFor the n valencys C optionally replaced3-20Cycloalkanes hydrocarbon ring, the n valencys C optionally replaced3-20Cyclenes hydrocarbon ring or
The n valencys C optionally replaced2-20Heterocycle；The divalent C that n-1 group B is each independently singly-bound, optionally replaces3-20Cycloalkanes hydrocarbon ring is appointed
Choose the divalent C in generation3-20Cyclenes hydrocarbon ring, the divalent C optionally replaced6-20Aromatic ring, the divalent C optionally replaced4-20Hetero-aromatic ring, optionally substitution
Divalent C2-20Heterocycle or the divalent combination group optionally replaced；When n-1 group B is each independently singly-bound, optionally substitution
Divalent C3-20Cycloalkanes hydrocarbon ring, the divalent C optionally replaced3-20Cyclenes hydrocarbon ring or the divalent C optionally replaced2-20During heterocycle, n-1 base
The divalent aliphatic hydrocarbon chain that group R is each independently singly-bound or optionally replaces；When n-1 group B is each independently optional substitution
Divalent C6-20Aromatic ring, the divalent C optionally replaced4-20When hetero-aromatic ring or the divalent combination group optionally replaced, n-1 group R is each
From independently being the divalent aliphatic hydrocarbon chain that optionally replaces；Aliphatic hydrocarbon chain in each definition is each independently selected from C1-15It is full
And/or undersaturated linear chain or branch chain hydrocarbon chain；When the carbon atom number of the aliphatic hydrocarbon chain is more than 2 and is wrapped in its strand
When containing C -- C single bond, insertion-O- ,-S- or-NR optionally between two carbon atoms of the C -- C single bond1, wherein R1It is H or C1-4
Linear or branched alkyl group；N is 2 to 10 integer,
Term " combination group " refers to two or more C3-20Cycloalkanes hydrocarbon ring bonds together via singly-bound or linking group and is formed
Group, two or more C3-20Group that cyclenes hydrocarbon ring bonds together via singly-bound or linking group and formed, two or
Multiple C6-20Group that aromatic ring bonds together via singly-bound or linking group and formed, two or more C4-20Hetero-aromatic ring via
Group that singly-bound or linking group bond together and formed, two or more C2-20Heterocycle via singly-bound or linking group that
This group or C for being bonded and being formed3-20Cycloalkanes hydrocarbon ring, C3-20Cyclenes hydrocarbon ring, C6-20Aromatic ring, C4-20Hetero-aromatic ring and C2-20Heterocycle
In it is two or more by condensing or bonding together and the group formed via singly-bound or linking group each other,
Term " linking group " refers to-O-；-S-；-NR1, wherein R1It is H or C1-4Linear or branched alkyl group；Optionally replace
C1-4Linear chain or branch chain alkylidene；The C optionally replaced2-4Linear chain or branch chain alkenylene；The C optionally replaced2-4Linear chain or branch chain Asia alkynes
Base；Or the arbitrary combination of these linking groups, but-O- ,-S- and-NR1Except situation about being bonded with itself or directly with one another,
Statement " optionally replacing " is referred to optionally by one or more selected from halogen, hydroxyl, sulfydryl, amino, amino carbonyl, nitre
Base, oxo, thio, cyano, C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-6Linear chain or branch chain (halogenated) alkene
(oxygen, sulphur, ammonia, carbonyl) base, C2-6Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl, C3-20Cycloalkanes (oxygen,
Sulphur, ammonia) base, C3-20Cycloalkyl C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Straight chain or branch
Chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkyl C2-6Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C3-20
Cycloalkenyl group, C3-20Cyclenes (oxygen, sulphur, ammonia) base, C3-20Cycloalkenyl group C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base,
C3-20Cycloalkenyl group C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C3-20Cycloalkenyl group C2-6Linear chain or branch chain (halogenated) alkynes
(oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl, C6-20Fragrant (oxygen, sulphur, ammonia) base, C6-20Aryl C1-6Linear chain or branch chain (halogenated) alkane (oxygen,
Sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C6-20Aryl C2-6Linear chain or branch chain
(halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl, C4-20Heteroaryl (oxygen, sulphur, ammonia) base, C4-20Heteroaryl C1-6Straight chain or branch
Chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C4-20Heteroaryl C2-6Linear chain or branch chain (halogenated) alkene (oxygen, sulphur, ammonia, carbonyl) base, C4-20
Heteroaryl C2-6Linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle, C2-20Heterocycle (oxygen, sulphur, ammonia) base,
C2-20Heterocycle C1-6Linear chain or branch chain (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base, C2-20Heterocycle C2-6Linear chain or branch chain (halogenated) alkene
(oxygen, sulphur, ammonia, carbonyl) base and C2-20Heterocycle C2-6The substituent group substitution of linear chain or branch chain (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base,
Wherein these substituent groups there are it is multiple when, can bond together and be formed the substituent group of divalent between adjacent two substituent groups
Structure,
Statement " (halogenated) alkane (oxygen, sulphur, ammonia, carbonyl) base " is meant that：Alkyl, halogenated alkyl, alkoxy, alkylthio group, alkylamino,
Alkyl-carbonyl, halogenated alkoxy, halogenated alkylthio, halogenated alkylamino or halogenated alkyl carbonyl, statement " (halogenated) alkene (oxygen,
Sulphur, ammonia, carbonyl) base " it is meant that：Alkenyl, halogenated alkenyl, alkenyloxy group, alkenylthio group, enamino, alkenyl carbonyl, haloalkenyloxy,
Halogenated alkenylthio group, halogenated enamino or halogenated alkenyl carbonyl, statement " (halogenated) alkynes (oxygen, sulphur, ammonia, carbonyl) base " are meant that：
Alkynyl, halo alkynyl, alkynyloxy group, alkynes sulfenyl, alkynes amino, alkynylcarbonyl groups, halogenated alkynyloxy group, acetylenic halide sulfenyl, acetylenic halide amino
Or halo alkynyl carbonyl, statement " (oxygen, sulphur, ammonia) base " is meant that, oxygroup, sulfenyl or amino, wherein the halogenated packet
Include one halogenated, dihalo, three halogenated or perhalogenos.
2. the manufacturing method of the nitrile of claim 1, wherein making carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2AUnder connect
Touch the reaction time of 0.05-2 hours.
3. the manufacturing method of the nitrile of claim 1, wherein making carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2AUnder connect
Touch the reaction time of 0.1-1.5 hours.
4. the manufacturing method of the nitrile of claim 1, wherein making carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2AUnder connect
Touch the reaction time of 0.2-1 hours.
5. the manufacturing method of the nitrile of claim 1, wherein making carboxylic acid sources with the ammonia source in the reaction temperature T from T1 to T2AUnder connect
Touch the reaction time of 0.3-0.8 hours.
6. the manufacturing method of the nitrile of claim 1, wherein T2-T1 >=10 DEG C.
7. the manufacturing method of the nitrile of claim 1, wherein by the amide intermediate product in the reaction temperature T from T3 to T4BLower heat
The reaction time of processing 0.2 to 3 hour.
8. the manufacturing method of the nitrile of claim 1, wherein by the amide intermediate product in the reaction temperature T from T3 to T4BLower heat
The reaction time of processing 0.3 to 2 hour.
9. the manufacturing method of the nitrile of claim 1, wherein by the amide intermediate product in the reaction temperature T from T3 to T4BLower heat
The reaction time of processing 0.4 to 1.2 hour.
10. the manufacturing method of the nitrile of claim 1, wherein by the amide intermediate product in the reaction temperature T from T3 to T4BUnder
The reaction time of heat treatment 0.4 to 1 hour.
11. the manufacturing method of the nitrile of claim 1, wherein T4-T3 >=10 DEG C.
12. the manufacturing method of the nitrile of claim 1, wherein the reaction temperature TAFor from T1 ' to T2 ', wherein T1 '=T1+5 DEG C,
Or T1+10 DEG C or T1+20 DEG C or T1+30 DEG C or T1+40 DEG C or T1+50 DEG C or T1+60 DEG C or
T1+70 DEG C or T1+80 DEG C or T1+90 DEG C, T2 '=T2 or T2-5 DEG C or T2-10 DEG C or T2-20 DEG C or
T2-30 DEG C or T2-40 DEG C or T2-50 DEG C or 310 DEG C of person, on condition that T2 ' ＞ T1 '；The reaction temperature TBFor from
T3 ' to T4 ', wherein T3 '=T3+5 DEG C or T3+10 DEG C or T3+20 DEG C or T3+30 DEG C or T3+40 DEG C or
T3+50 DEG C or T3+60 DEG C or T3+70 DEG C or T3+80 DEG C, T4 '=T4 or T4-5 DEG C or T4-10 DEG C or
T4-20 DEG C or T4-30 DEG C or T4-40 DEG C or T4-50 DEG C or 350 DEG C of person, on condition that T4 ' ＞ T3 '.
13. the manufacturing method of the nitrile of claim 1, wherein T1 for 145 DEG C either 150 DEG C either 160 DEG C or 170 DEG C or
180 DEG C of person either 190 DEG C of either 200 DEG C of either 210 DEG C of either 220 DEG C of either 230 DEG C either 240 DEG C or 250
DEG C either 260 DEG C of either 270 DEG C of either 280 DEG C either 290 DEG C or 300 DEG C；T2 for 310 DEG C either 300 DEG C or
290 DEG C of either 280 DEG C of either 270 DEG C of either 260 DEG C of either 250 DEG C of either 240 DEG C either 230 DEG C or 220 DEG C,
Either 210 DEG C of either 200 DEG C either 190 DEG C or 180 DEG C；T3 is 225 DEG C of either 230 DEG C either 240 DEG C or 250
DEG C either 260 DEG C of either 270 DEG C of either 280 DEG C of either 290 DEG C either 300 DEG C or 310 DEG C；T4 for 350 DEG C or
340 DEG C of either 330 DEG C of either 320 DEG C of either 310 DEG C of either 300 DEG C of either 290 DEG C either 280 DEG C or 270 DEG C.
14. the manufacturing method of the nitrile of claim 1, wherein the second step is in open reactive system or closed reaction
It is carried out in system.
15. the manufacturing method of the nitrile of claim 1, wherein catalyst, and the second step is not used in the first step
Progress or unused catalyst in the presence of a catalyst.
16. the manufacturing method of the nitrile of claim 1, wherein the ammonia source is industrial waste ammonia gas.
17. the manufacturing method of the nitrile of claim 1, wherein the carboxylic acid sources be carboxylic acid shown in following table, the carboxylic acid acid anhydrides or
Methyl esters, in the first step, reaction temperature TAAs shown in the table, the reaction time is 0.05-2 hours, in the second step
In rapid, reaction temperature TBAs shown in the table, the reaction time is 0.2 to 3 hour,
18. the manufacturing method of the nitrile of claim 17, wherein in the first step, the reaction time is 0.1-1.5 hours.
19. the manufacturing method of the nitrile of claim 17, wherein in the first step, the reaction time is 0.2-1 hours.
20. the manufacturing method of the nitrile of claim 17, wherein in the first step, the reaction time is 0.3-0.8 hours.
21. the manufacturing method of the nitrile of claim 17, wherein in the second step, the reaction time is 0.3 to 2 hour.
22. the manufacturing method of the nitrile of claim 17, wherein in the second step, the reaction time is 0.4 to 1.2 hour.
23. the manufacturing method of the nitrile of claim 17, wherein in the second step, the reaction time is 0.4 to 1 hour.
24. the manufacturing method of the nitrile of claim 1, wherein the aliphatic hydrocarbon chain in each definition is each independently selected from C1-15Straight chain
Or branched alkane hydrocarbon chain, C2-15Linear chain or branch chain alkene chain or C2-15Linear chain or branch chain alkynes chain.
25. the manufacturing method of the nitrile of claim 24, wherein the aliphatic hydrocarbon chain is each independently selected from C1-9Linear chain or branch chain
Alkane chain, C2-9Linear chain or branch chain alkene chain or C2-9Linear chain or branch chain alkynes chain.
26. the manufacturing method of the nitrile of claim 1, wherein n are 2 to 4 integers.
27. the manufacturing method of the nitrile of claim 1, wherein the first step is gone back while the amide intermediate product is obtained
Effluent containing ammonia is obtained, and using the supplement as the ammonia source in the circulation-supplied to the first step of effluent containing ammonia
An or part.
28. the manufacturing method of the nitrile of claim 27, wherein the effluent containing ammonia is by concentration or dry Posterior circle supply
Supplement or a part into the first step as the ammonia source.
29. the manufacturing method of the nitrile of claim 1, wherein carboxylic acid sources in terms of carboxyl with NH3It rubs in the ammonia source of meter
You are than minimum 1: 20, up to 1: 500.
30. the manufacturing method of the nitrile of claim 1, wherein carboxylic acid sources in terms of carboxyl with NH3It rubs in the ammonia source of meter
You are than minimum 1: 40, up to 1: 300.
31. the manufacturing method of the nitrile of claim 1, wherein carboxylic acid sources in terms of carboxyl with NH3It rubs in the ammonia source of meter
You are than minimum 1: 50, up to 1: 80.
32. the manufacturing method of the nitrile of claim 1, wherein the carboxylic acid sources use industrial corresponding crude product.
33. the manufacturing method of the nitrile of claim 1, wherein the carboxylic acid sources are biological sources.
34. the manufacturing method of the nitrile of claim 1, wherein the first step and the second step are in same reaction vessel
Middle progress carries out in different reaction vessels.
35. the manufacturing method of the nitrile of claim 1, wherein the second step carries out in closed reaction system.
36. the manufacturing method of the nitrile of claim 1, wherein the ammonia content in the ammonia source is 85-95wt%.
37. a kind of manufacturing method of amine, which is characterized in that include the following steps：
First step：Nitrile is manufactured according to the manufacturing method of any one of claims 1 to 36；With
Second step：The nitrile of first step acquisition is hydrogenated to manufacture amine.
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| CN1210852A (en) * | 1997-08-06 | 1999-03-17 | 东丽株式会社 | Process for producing nitrile |
| CN102249949A (en) * | 2011-05-13 | 2011-11-23 | 奇凯（大连）化工有限公司 | Preparation method of cyclopropyl fenpropathin derivative |
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| EP2714682B1 (en) * | 2011-05-24 | 2016-03-16 | Università degli Studi di Bari "Aldo Moro" | Novel tetrahydroisoquinoline compounds for use in the diagnosis and treatment of neurodegenerative diseases |
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| CN1210852A (en) * | 1997-08-06 | 1999-03-17 | 东丽株式会社 | Process for producing nitrile |
| CN102249949A (en) * | 2011-05-13 | 2011-11-23 | 奇凯（大连）化工有限公司 | Preparation method of cyclopropyl fenpropathin derivative |
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| Vibrational Circular Dichroism of Optically Active Cyclopropanes. Experimental Results;V. J. Heintz et al.;《Journal of the American Chemical Society》;19811231;第103卷(第9期);2395-2403 * |
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