CN105131031B - Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction - Google Patents
Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction Download PDFInfo
- Publication number
- CN105131031B CN105131031B CN201510395880.1A CN201510395880A CN105131031B CN 105131031 B CN105131031 B CN 105131031B CN 201510395880 A CN201510395880 A CN 201510395880A CN 105131031 B CN105131031 B CN 105131031B
- Authority
- CN
- China
- Prior art keywords
- hydrocarbylthio
- reactor
- synthesizes
- reaction
- phosphoric triamides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a method for synthesizing N-alkylthiophosphoryl triamide through a continuous reaction. The method comprises the following steps: 1, mixing thiophosphoryl chloride with an organic solvent, pre-cooling the obtained mixture in a heat exchanger to -5-0DEG C, mixing the material with an aminated compound pre-cooled to -5-0DEG C, and reacting the obtained mixture in a micro-reactor to obtain N-alkylthiophosphoryl dichloride at the outlet of the reactor; and 2, allowing N-alkylthiophosphoryl dichloride to directly enter an ammoniation reactor, carrying out an ammoniation reaction on N-alkylthiophosphoryl dichloride and ammonia gas, and post-processing after the ammoniation reaction is completed to obtain N-alkylthiophosphoryl triamide. N-alkylthiophosphoryl triamide is synthesized through a micro-reaction technology with high mass transfer and heat transfer efficiency, so conversion of intermittence to continuity is realized, the operating step is simplified, and the reaction yield is improved.
Description
Technical field
The invention belongs to chemosynthesis technical field, is related to the method that successive reaction synthesizes N- hydrocarbylthio phosphoric triamides.
Background technology
N-pro-pyl thiophosphoryl triamide, normal-butyl thiophosphoryl triamine are all effective soil urease inhibitor.They can
To mix the activity for suppressing soil urokinase with certain proportion with carbamide, the degradation speed of carbamide is greatly lowered, nitrogen is improved
Utilization rate, while the elements such as S, P are provided, with good soil improvement action.
The current synthetic method of N- hydrocarbylthio phosphoric triamides is substantially and carries out in a kettle., including two categories below side
Method:(1) two-step method, patent US4530714, US5883297 and CN101337976A disclose " two-step method " and prepare N- alkyl bases
The method of thiophosphoryl triamide, i.e., acid binding agent presence under conditions of or without acid binding agent under conditions of, by phosphorus thiochloride solution with
The direct hybrid reaction of alkylamine solution, or be obtained in the middle of N- alkylthio phosphinylidyne dichloros by the way of Deca alkylamine solution
Body, proceeds to another reactor after the intermediate is isolated and purified, lead to ammonia, and Jing process after reaction a period of time separates to obtain N- alkyl
Thiophosphoryl triamide.The complex process, is related to low-temp reaction and the response time is long, and energy consumption is big, and yield low cost is high;(2) one pots
Method, CN101412733A disclose the method that " one kettle way " prepares N- hydrocarbylthio phosphoric triamides, i.e., under conditions of acid binding agent,
Phosphorus thiochloride generates intermediate N hydrocarbylthio phosphinylidyne dichloro and acid binding agent hydrochlorate with alkyl uncle by reaction, then same
Reaction system is reacted with ammonia, generates target product N- hydrocarbylthio phosphoric triamides, acid binding agent and ammonium chloride.Although the technique is saved
Step is saved but has had to use acid binding agent, be that one kettle way increased post-processing difficulty, complex operation step again.
In addition, two-step reaction involved in the synthetic reaction is exothermic reaction, course of reaction is more violent, and with
Upper technique is carried out in a kettle., weak heat-dissipating and is difficult to avoid that back-mixing between reaction raw materials and product, therefore di-n-butyl sulfur
It is more for the by-product such as phosphoric triamide and three normal-butyl thiophosphoryl triamines.Therefore it is huge that process units is there is in production,
The problems such as post processing is difficult, environmental protection pressure increases.
The content of the invention
The invention provides a kind of method that successive reaction synthesizes N- hydrocarbylthio phosphoric triamides, the method increases reaction
Yield, operate simpler, and production efficiency is improved.
A kind of successive reaction synthesizes the method for N- hydrocarbylthio phosphoric triamides, comprises the steps:
(1) will phosphorus thiochloride and organic solvent mixing after be cooled to -5~0 DEG C in heat exchanger in advance, then again be cooled to -5 in advance
~0 DEG C of aminated compoundss mixing, the mixture of acquisition are reacted in microreactor, obtain N- alkyl from reactor outlet
Phosphorothioic dichlorides;
Described microreactor is microchannel reactor, and the internal diameter of described microchannel reactor is 10~500 μm;
The structural formula of described aminated compoundss is RNH2;
The structure of described N- hydrocarbylthio phosphinylidyne dichloros is as shown in formula II:
(2) the N- hydrocarbylthio phosphinylidyne dichloros that step (1) is obtained carry out ammonification with ammonia in being directly entered ammoniation reactor
Reaction, processes after Jing after aminating reaction is complete and obtains described N- hydrocarbylthio phosphoric triamides;
The structure of described N- hydrocarbylthio phosphoric triamides is as shown in formula I:
Wherein, R is selected from C1~C8Alkyl, C1~C8Cycloalkyl or benzyl.
Present invention employs the microchannel reactor of particular inside diameters continuously to synthesize N- hydrocarbylthio phosphinylidyne dichloros, the micro-pipe
Road reactor has higher mass transfer and heat transfer efficiency, meanwhile, pre-cooling is carried out to reaction raw materials in advance in the initial period of reaction,
Be effectively improved the yield of reaction, from microreactor outlet reactant liquor can be directly entered in ammoniation reactor without isolation with
Ammonia reaction generates N- hydrocarbylthio phosphoric triamides, and the production efficiency of whole continuous reaction process and safety are higher.
In step (1), the species of organic solvent can produce large effect to the yield for reacting, and described organic solvent is
At least one in ethyl acetate, toluene, chlorobenzene, dichloromethane, tetrahydrofuran and 2- methyltetrahydrofurans.Preferably, institute
The organic solvent stated is dichloromethane or tetrahydrofuran.
In step (1), it is that each raw material can fully react completely crucial, described trichlorine to control suitable flow-rate ratio
Sulfur phosphorus, organic solvent, the volume flow ratio of primary hydrocarbyl amine are 1:0.5~15:1.0~2.0, preferably 1:5~8:1.5~1.8.
Preferably, described R is n-pro-pyl, normal-butyl or isobutyl group.
In step (1), reactor cooled bath temperature is -20~0 DEG C, preferably -10 DEG C;
Stable reactor inlet temperatures are less than 35 DEG C, and the reactant liquor time of staying is 1~8min, preferably 2~4min.
Microchannel reactor of the described microreactor for multi-stage series, volume are 30ml~120ml.Per section series connection it is anti-
Answer device all to carry outlet, according to the degree that reaction is carried out, reactant liquor can be derived from different outlets.
It is 150~200 μm as the internal diameter of further preferred, described microchannel reactor, volume is 60~90ml,
The flow velocity of described phosphorus thiochloride is 2.5~3.5ml/min, and the flow velocity of described organic solvent is 14~21ml, described amine
The flow velocity of class chemical combination is 3.6~5.5ml/min.Now, the efficiency of reaction is greatly improved, and side reaction is significantly reduced.
Compared with the existing technology, beneficial effects of the present invention are embodied in:
(1) using the synthesis N- hydrocarbylthio phosphoric triamides of the micro-reacting tcchnology with higher mass transfer and heat transfer efficiency.Should
Method can realize that from interval to continuous conversion operating process is simple, and reaction yield is high.Production efficiency will be obtained with safety
Greatly improve;
(2) although 30 DEG C or so of the temperature sensor reading of Reactor inlet, and reactor outlet temperature all the time 5 DEG C with
Under, it was demonstrated that enough, thermal diffusivity is good for reactor exchange capability of heat;
(3) reactor can meet the use requirement under high temperature, high pressure operating mode.And based on the micro- anti-of modular design
Utensil is answered to have the advantages of motility is good, and reliability is high and easy to maintain.
Specific embodiment
Below in conjunction with technical scheme and the specific embodiment of the example in detail present invention, but the interior of invention can not be limited
Hold.
The preparation of 1 N- n-pro-pyl phosphorothioic dichlorides of embodiment
Phosphorus thiochloride (SPCl3), organic solvent (tetrahydrofuran THF or dichloromethane CH2Cl2) and n-propylamine (n-C3H9N)
Microreactor system is injected by plunger displacement pump respectively, phosphorus thiochloride and organic solvent are first via changing micro- after a blender mixing
Pre-cooling (- 5~0 DEG C) in hot device, is then mixed in a stacked blender with the n-propylamine (- 5~0 DEG C) through pre-cooling again,
The mixture of acquisition enters line delay reaction into the microchannel reactor of multi-stage series, and the internal diameter of every section of microchannel reactor is
200 μm, volume is 30mL, and every section of microchannel reactor is provided with independent outlet.Control reactor cooled bath temperature and reaction stop
Time, collection is stayed to obtain intermediate reaction liquid, contained N- n-pro-pyls phosphorothioic dichlorides carry out table using HPLC area normalization methods
Levy (the results are shown in Table 1).
The reaction condition of 1 embodiment 1 of table and result
The preparation of 2 N- normal-butyl phosphorothioic dichlorides of embodiment
(1) phosphorus thiochloride (SPCl3), organic solvent (tetrahydrofuran THF or dichloromethane CH2Cl2) and n-butylamine (n-
C4H11N microreactor system is injected by plunger displacement pump respectively), phosphorus thiochloride and organic solvent first via a blender mixing after
Pre-cooling (- 5~0 DEG C) in micro- heat exchanger, then again with the n-propylamine (- 5~0 DEG C) through pre-cooling in a stacked blender
Mixing, the mixture of acquisition enter line delay reaction into the microchannel reactor of multi-stage series, every section of microchannel reactor it is interior
Footpath is 150 μm, and volume is 30mL, and every section of microchannel reactor is provided with independent outlet.Control reactor cooled bath temperature and anti-
Answer the time of staying, collection obtains intermediate reaction liquid, and contained N- normal-butyls phosphorothioic dichlorides are entered using HPLC area normalization methods
Row characterizes (the results are shown in Table 2).
(2) the intermediate reaction liquid that step (1) is obtained is passed directly in the ammoniation reactor equipped with dichloromethane, at 25 DEG C often
Pressure is reacted with ammonia, and after reaction completely, add water stirring 1 hour, stratification, organic solvent vacuum distillation recovered solvent
Afterwards, residue adds mixed solvent (dichloromethane:Petroleum ether=1:1) it is cooled to -5~0 DEG C of crystallization and obtains the thio phosphorus of normal-butyl
Acyl triamine sterling, is white crystal, and yield and purity are shown in Table 2.
The reaction condition of 2 embodiment 2 of table and result
The preparation of 3 N- isobutylthio phosphinylidyne dichloros of embodiment
Phosphorus thiochloride (SPCl3), organic solvent (tetrahydrofuran THF or dichloromethane CH2Cl2) and isobutyl amine (i-C4H11N)
Microreactor system is injected by plunger displacement pump respectively, phosphorus thiochloride and organic solvent are first via changing micro- after a blender mixing
Pre-cooling (- 5~0 DEG C) in hot device, is then mixed in a stacked blender with the n-propylamine (- 5~0 DEG C) through pre-cooling again,
The mixture of acquisition enters line delay reaction into the microchannel reactor of multi-stage series, and the internal diameter of every section of microchannel reactor is
150 μm, volume is 30mL, and every section of microchannel reactor is provided with independent outlet.Control reactor cooled bath temperature and reaction stop
Time, collection is stayed to obtain intermediate reaction liquid, contained N- isobutylthio phosphinylidyne dichloros carry out table using HPLC area normalization methods
Levy (the results are shown in Table 3).
The reaction condition of 3 embodiment 3 of table and result
Comparative example 1
(1) phosphorus thiochloride (SPCl3), organic solvent (tetrahydrofuran THF or dichloromethane CH2Cl2) and n-butylamine (n-
C4H11N microreactor system is injected by plunger displacement pump respectively), phosphorus thiochloride and organic solvent are first via under a blender room temperature
Mixing, is then mixed in a stacked blender with n-propylamine again at room temperature, and the mixture of acquisition enters multi-stage series
Microchannel reactor enters line delay reaction, and the internal diameter of every section of microchannel reactor is 150 μm, and volume is 30mL, every section of microchannel
Reactor is provided with independent outlet.Control reactor cooled bath temperature and reaction time, collection obtain intermediate reaction liquid, institute
The N- normal-butyls phosphorothioic dichlorides for containing are characterized (the results are shown in Table 4) using HPLC area normalization methods.
(2) the intermediate reaction liquid that step (1) is obtained is passed directly in the ammoniation reactor equipped with dichloromethane, at 25 DEG C often
Pressure is reacted with ammonia, and after reaction completely, add water stirring 1 hour, stratification, organic solvent vacuum distillation recovered solvent
Afterwards, residue adds mixed solvent (dichloromethane:Petroleum ether=1:1) it is cooled to -5~0 DEG C of crystallization and obtains the thio phosphorus of normal-butyl
Acyl triamine sterling, is white crystal, and yield and purity are shown in Table 4.
Comparative example 2
(1) phosphorus thiochloride (SPCl3), organic solvent (tetrahydrofuran THF or dichloromethane CH2Cl2) and n-butylamine (n-
C4H11N microreactor system is injected by plunger displacement pump respectively), phosphorus thiochloride and organic solvent first via a blender mixing after
Pre-cooling (- 5~0 DEG C) in micro- heat exchanger, then again with the n-propylamine (- 5~0 DEG C) through pre-cooling in a stacked blender
Mixing, the mixture of acquisition enter line delay reaction into the microchannel reactor of multi-stage series, every section of microchannel reactor it is interior
Footpath is 600 μm, and volume is 30mL, and every section of microchannel reactor is provided with independent outlet.Control reactor cooled bath temperature and anti-
Answer the time of staying, collection obtains intermediate reaction liquid, and contained N- normal-butyls phosphorothioic dichlorides are entered using HPLC area normalization methods
Row characterizes (the results are shown in Table 4).
(2) the intermediate reaction liquid that step (1) is obtained is passed directly in the ammoniation reactor equipped with dichloromethane, at 25 DEG C often
Pressure is reacted with ammonia, and after reaction completely, add water stirring 1 hour, stratification, organic solvent vacuum distillation recovered solvent
Afterwards, residue adds mixed solvent (dichloromethane:Petroleum ether=1:1) it is cooled to -5~0 DEG C of crystallization and obtains the thio phosphorus of normal-butyl
Acyl triamine sterling, is white crystal, and yield and purity are shown in Table 4.
Reaction condition and the result of 4 comparative example 1 of table and comparative example 2
From the result of comparative example 1, if without precooling step, the reaction efficiency of step (1) is greatly lowered;It is right
The result explanation of ratio 2, when the internal diameter of pipeline is bigger, reaction effect is significantly reduced.
Claims (9)
1. a kind of method that successive reaction synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that comprise the steps:
(1) will phosphorus thiochloride and organic solvent mixing after be cooled to -5~0 DEG C in heat exchanger in advance, then again be cooled to -5~0 in advance
DEG C aminated compoundss mixing, the mixture of acquisition reacted in microreactor, obtains N- alkyl sulfur from reactor outlet
For phosphinylidyne dichloro;
Described microreactor is microchannel reactor, and the internal diameter of described microchannel reactor is 10~500 μm;Reactor is cold
But bath temperature is -20~0 DEG C;Stable reactor inlet temperatures are less than 35 DEG C, and the reactant liquor time of staying is 1~8min;
The structural formula of described aminated compoundss is RNH2;
The structure of described N- hydrocarbylthio phosphinylidyne dichloros is as shown in formula II:
(2) the N- hydrocarbylthio phosphinylidyne dichloros that step (1) is obtained carry out aminating reaction with ammonia in being directly entered ammoniation reactor,
Process after Jing after aminating reaction is complete and obtain described N- hydrocarbylthio phosphoric triamides;
The structure of described N- hydrocarbylthio phosphoric triamides is as shown in formula I:
Wherein, R is selected from C1~C8Alkyl, C1~C8Cycloalkyl or benzyl.
2. the method that successive reaction according to claim 1 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that step
(1) in, during described organic solvent is ethyl acetate, toluene, chlorobenzene, dichloromethane, tetrahydrofuran and 2- methyltetrahydrofurans
At least one.
3. the method that successive reaction according to claim 2 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that described
Organic solvent be dichloromethane or tetrahydrofuran.
4. the method that successive reaction according to claim 1 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that step
(1), in, described phosphorus thiochloride, organic solvent, the volume flow ratio of primary hydrocarbyl amine are 1:0.5~15:1.0~2.0.
5. the method that successive reaction according to claim 4 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that described
Phosphorus thiochloride, organic solvent, primary hydrocarbyl amine volume flow ratio be 1:5~8:1.5~1.8.
6. the method that successive reaction according to claim 1 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that step
(1), in, described R is n-pro-pyl, normal-butyl or isobutyl group.
7. the method that successive reaction according to claim 1 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that reaction
Device cooling bath temperature is -10 DEG C, and the reactant liquor time of staying is 2~4min.
8. the method that successive reaction according to claim 1 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that step
(1), in, described microreactor is the microchannel reactor of multi-stage series, and cumulative volume is 30ml~120ml.
9. the method that successive reaction according to claim 8 synthesizes N- hydrocarbylthio phosphoric triamides, it is characterised in that described
Microreactor cumulative volume be 60~90ml.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510395880.1A CN105131031B (en) | 2015-07-03 | 2015-07-03 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510395880.1A CN105131031B (en) | 2015-07-03 | 2015-07-03 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105131031A CN105131031A (en) | 2015-12-09 |
CN105131031B true CN105131031B (en) | 2017-03-22 |
Family
ID=54716654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510395880.1A Active CN105131031B (en) | 2015-07-03 | 2015-07-03 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105131031B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111808132A (en) * | 2019-04-11 | 2020-10-23 | 西南科技大学 | Method for continuously and rapidly preparing N-phenyl thiophosphoryl dichloride by using microreactor |
CN110950904B (en) * | 2019-11-12 | 2023-05-05 | 武威金仓生物科技有限公司 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ302400B6 (en) * | 2008-10-20 | 2011-05-04 | Agra Group, A.S. | Process for preparing N-(hydrocarbyl)triamides of phosphoric or thiophosphoric acid |
CN101525348A (en) * | 2009-04-07 | 2009-09-09 | 林文斌 | Method for industrialized production of N-alkyl substituted phosphoric triamide |
CN104370957A (en) * | 2014-10-28 | 2015-02-25 | 浙江奥复托化工有限公司 | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide |
-
2015
- 2015-07-03 CN CN201510395880.1A patent/CN105131031B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN105131031A (en) | 2015-12-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101981040B (en) | Process for the preparation of triamides from ammonia and amidodichlorides | |
CN103755739A (en) | Continuous production method for N-NBPT | |
CN102030775B (en) | Method for producing N-(N-butyl)thiophosphoric triamide in channelization manner and special equipment | |
EA015237B1 (en) | Method for lithium exchange reactions | |
CN105131031B (en) | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction | |
CN101307084A (en) | Synthetic process of decitabine | |
CN105399768B (en) | A kind of process for cleanly preparing for preparing N normal-butyl thiophosphoryl triamines | |
CN110105392A (en) | What a kind of tenofovir Chinese mugwort drew phenol amine efficiently synthesizes technique | |
CN104370957A (en) | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide | |
CN105646368A (en) | Preparation method of 2, 4-dichloro-5-methoxy pyrimidine | |
JP4861835B2 (en) | Method for producing imide ether compound | |
CN108084224A (en) | A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines | |
CN102557952B (en) | Method for preparing di-tert-butyl dicarbonate | |
CN114746397A (en) | Continuous flow process for the synthesis of hydroxamic acids | |
CN105399767A (en) | Production method of N-alkyl substituted phosphoric triamide | |
CN103664952A (en) | Preparation method of zopiclone | |
CN107098936A (en) | A kind of preparation method of TAF nucleoside derivates | |
CN110950904B (en) | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide | |
CN106083693A (en) | The N phthalyl synthesis technique to (dihydroxy ethyl) amino L phenylalanine ethyl ester | |
CN106008392A (en) | Preparation method for intermediate of anti-cancer drug dasatinib | |
CN104945434A (en) | (2-disubstituted phosphino-phenyl)-1-alkyl-indol-phosphine ligand and synthetic method and application thereof | |
CN108610330B (en) | Chloropyridyl bridged bistetrazole compound and synthesis and application thereof | |
CN109456376A (en) | The novel processing step of 5 '-DMTr-2 '-EOE-5-Me- cytidine of nucleosides modifier | |
CN104478762B (en) | Preparation method of N,O-dimethyl-N-nitroisourea | |
CN114853756B (en) | Preparation process of compound Tomivosertib |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CP03 | Change of name, title or address | ||
CP03 | Change of name, title or address |
Address after: 312369 Hangzhou Bay Shangyu economic and Technological Development Zone, Zhejiang, Shaoxing Patentee after: Zhejiang today Hui new materials Limited by Share Ltd Address before: 312369, No. five, No. 2, Shangyu Industrial Park, Hangzhou Bay, Zhejiang, Shaoxing Patentee before: SHANGYU SUNFIT CHEMICAL CO., LTD. |