Basic Guidelines For Microwave Reactor and Reactions

Basic Guidelines for Microwave Organic Chemistry Applications
By Laura Favretto
Microwave Organic Chemistry Application Specialist
MicroSYNTH
START
UNI EN ISO 9001:2000 Vision certified
Basic Guidelines for Microwave Organic Chemistry Applications Rev. 0/04 Milestone Srl
Basic Guidelines for Microwave Organic Chemistry Application
INDEX 1. 2. Introduction How to convert a conventional reaction into a microwave reaction Solvent Temperature-Time Vessel Microwave program Stirring When and how to use Weflon How to regulate microwave power How to optimize the microwave program How to optimize the reaction condition How to use the rotor When it is possible to open the reactor What to do when an exothermic is present Page 2
Page 3 Page 3 Page 4 Page 5 Page 6 Page 6 Page 7 Page 8 Page 9 Page 9 Page 10 Page 10
3. 4. 5. 6. 7. 8. 9.
10. Is it possible to use microwave at constant power 11. How to perform solid state reaction 12. How to work with metal powder (heterogeneous solution) 13. Maximum heating time 14. Which chemistry is not suitable for microwave 15. Solvent Library Solvent List Solvent Graphics
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Page 13 Page 13
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Page 15 Page 28
Basic Guidelines for Microwave Organic Chemistry Application Rev. 0/04 Milestone Srl
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1. INTRODUCTION The main advantages of microwave assisted organic synthesis are: a) Faster reaction: the microwave can use higher temperatures than conventional heating system, and consequently the reactions are completed in few minutes instead of hours. b) Better yield and higher purity: less formation of side product are observed using microwave irradiation, and the product is recovered in higher yield. Consequently, also the purification step is faster and easier. c) Easy scale-up: MicroSYNTH, with its technology and large range of reactor vessels, allows scale-up from few milliliters to one liter without changing reaction parameters. d) Reproducibility: the patented microwave diffuser for homogeneous microwave irradiation inside the cavity and precise control of reaction parameters, such as temperature, pressure and power, always reproduces the same reaction conditions. It is very simple to save and use an optimized synthesis method. e) Easy to use: all the reactors and software are very easy to use and all reactions can be easily moved from conventional to microwave heating.
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2. HOW TO CONVERT A CONVENTIONAL REACTION INTO A MICROWAVE REACTION When the reaction is performed the first time under microwave irradiation, run the reaction in small scale, slowly increasing the temperature. The parameters that are needed to be defined are: - solvent - temperature-time - vessel - microwave program Solvent The same solvent that is usually used with conventional heating chemistry can also be used with microwave heating. Solvents interact differently with microwaves, depending on their polarity. Polar solvents (alcohols, DMF, water, ketone, acid) couple well with microwaves and reach high temperatures in a short time. Non-polar solvents (toluene, chloroform, hexane) are transparent to microwaves. Therefore, two situations are possible: 1) non polar solvent, but polar reagents or at least one polar reagent: the reaction mixture is heated by microwave. 2) non polar reaction mixture (both solvent and reagents). (Weflon has to be added in order to heat the mixture. For more information, see chapter 3 When and how to use Weflon).
Temperature-Time a) If the reaction has already been performed with conventional heating, take in consideration the standard reaction temperature and time. Based on these two parameters, consider the Arrhenius equation, e.g. how the time decreases when the temperature increases. This law defines that every ten degrees that the temperature increases, the time of the reaction is halved.
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For example, if a reaction is run in EtOH at 80C for 8 hours and the Arrhenius law is applied, the time is reduced in accordance to the table below:
Temperature Time (C) 80 90 100 110 120 130 140 150 8h 4h 2h 60 min 30 min 15 min 8 min 4 min
By increasing the temperature of 70C, the time is reduced from 8 hours (480 minutes) to 4 minutes. This simple procedure can be applied to all the reactions. b) If the reaction has never been performed before with conventional or microwave heating, fix the temperature at 30-40C higher than the boiling point of the solvent, and run the reaction for 10 minutes. Then check the obtained reaction mixture.
Vessel All reactors that work with the MicroSYNTH have different: a) volume limit b) temperature limit c) pressure limit When the target temperature is fixed, consult the solvent library in chapter 15 (also present in the EasyWAVE software). Check which vapor pressure is developed from the solvent at the chosen temperature. Based on this value, and on the volume that is needed, decide the appropriate reactor vessel.
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Example: The target temperature of the reaction is 150C in EtOH. Based on the solvent library and on the graphic temperature vs. pressure (see graphic below), it is possible to predict that a pressure of 10 bar will be developed during the reaction.
If the reaction is completely unknown, and there is possible exothermic reaction or development of gas during the test, use the vessel with the highest specification of temperature and pressure (for example the 100 ml High Pressure reactor (Tmax = 250C, pmax = 55 bar)).
Microwave program The microwave program usually consists of two steps: The first step is the ramp to reach the target temperature. The second step is to keep the temperature for the desired reaction time. The second step is always the same for all sample amounts. In any case, a maximum total program time of 1 hour is advised. The first step must be regulated on the base of: - sample amount - characteristics of solvent
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- Polar mixture: - small amount (up to 30 mL): the increasing of the temperature can be fixed in the rate 25C/min. For example a suitable ramp for 15 mL of DMF could be
Time Power Temperature (C) (min) (Watt) 6 500 room temp to190 Step1
- large amount (more than 30 mL): the first step needs to be longer. In this case, its advised an increase of 10C/min - Non polar mixture: see the below When and how to use Weflon . Stirring Always put a stir bar in every reactor/vessel when a reaction is run. This enhances temperature, and therefore, reaction uniformity.
3) WHEN AND HOW TO USE WEFLON When the reaction mixture (reagents and solvent) are not polar, the Weflon is necessary in order to heat the solution. When Weflon is used, its necessary to use low value of microwave power and long heating ramp. This is necessary as there is a time lapse due to the transfer of heat from the Weflon to the solution. In this case, its advised to build the ramp with 4 steps: ramp up to the boiling point of the solvent with a rate of 15C/min and keep the temperature for 1-2 minutes; ramp up to the fixed temperature with a rate of 5C/min and keep the temperature for the desired time. The maximum power value to use is 500 Watt. If Weflon is used in one vessel, then it should be used in every vessel when processing multiple reactions simultaneously.
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An example of Toluene heating ramp with Weflon is reported below: MonoPREP P/N MOP0000, 20 mL of toluene in P/N QRS1550, stirring bar P/N 86116 and Weflon button P/N WO1703: Time Power Temperature (min) (Watt) (C) 5 500 110 2 400 110 15 500 160 5 500 160
Step1 Step2 Step3 Step4
Below is the temperature profile of 20 mL of Toluene

Toluene,20 mL, 160C
200 1,000 900 800 150
[3] 160 [4] 160
Te m pe ra ture [C]
700
[1] 110 [2] 110
600 500 400 300
100
50
20
200 100
0 00:05:00 00:10:00 00:15:00 00:20:00 00:25:00 00:30:00

Time [hh:mm:ss] T1 Set Values Pow er Temp. 1 Temp. 2
0 00:35:00
If the temperature is not following the temperature profile, change the time using longer ramp, but do not increase the power.
4) HOW TO REGULATE THE MICROWAVE POWER The value of the maximum microwave power depends on the amount of sample and of the number of reaction vessel. Up to 30 mL of volume and/or up to three vessels, 400-500 Watt of microwave power is enough to heat the reaction mixture. If the temperature is not following the designed temperature profile, use longer heating time (step n. 1), but do not increase the power.
P ow e r [W a tt]
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For example: MonoPREP with 15 mL of water: Time Power Temperature (min) (Watt) (C) 3 400 150 Step1 5 300 150 Step2
When large volume or more than three reactors are used with the rotor, its better to use an higher value of power (about 700-800 watt) and longer heating ramp. For example: PRO-6 with 15 mL of water in each vessel, use the following heating program: Time Power Temperature (min) (Watt) (C) 10 800 150 5 700 150
Step1 Step2
PRO-24 with 10 ml of isopropanol in each vessel, use the following heating program: Time Power Temperature (min) (Watt) (C) 16 1000 150 10 800 150
Step1 Step2
5) HOW TO OPTIMIZE A MICROWAVE PROGRAM 1) if the temperature doesnt follow the designed profile, make the ramp longer and/or increase the power. 2) if during the heating ramp the temperature overshoots, reduce the value of microwave power of about 100-150 Watt.
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In any case, remember that at high temperatures the solvents change their behavior. In general, their polarity decreases and they require more power to reach the desired temperature. For this reason, temperature spikes may be present at the beginning, but decrease or disappear at higher temperatures.
6) HOW TO OPTIMIZE THE REACTION CONDITIONS After the first run of the reactions, there could be four different cases: 1) the reaction is complete (the starting material is not present any more): transfer the mixture in a proper glassware and proceed with the usual work-up of the reaction 2) the reaction starts to work but is not complete (some starting material is still present): - extend the reaction time - increase the temperature (not over the temperature and pressure limit of the vessel) 3) the reaction doesnt work at all: - extend the time - increase the temperature - use more equivalent of one of the starting material or of the catalyst 4) decomposition of the reagents: - use lower temperature - use short reaction time Note: always remember to check the temperature and pressure limit of the vessel before increasing the temperature.
7) HOW TO USE THE ROTOR When a rotor is utilized (with multiple vessels), it is necessary to use - the same solvent in all the vessels - similar chemistry, i.e. same reaction, changing only one substituent of one reagent at time Temperature and pressure are measured in one vessel, called reference vessel. This ensures the same conditions of temperature and pressure in all the vessels of the rotor.
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For example, if the Heck reaction is considered:

Br Pd(OAc)2, PPh3 + R MeOOC DMF R COOMe
Heck reaction
R = - OMe - NO2 - Cl -H - CHO The nature of the group R- in the aryl bromide compound could be changed in each vessel in order to verify how the R- substituent influences the coupling reaction. If the catalyst varies from vessel to vessel, use the high concentration of catalyst in the reference vessel. In fact, the higher concentration of catalyst is usually the most reactive one, and needs to be controlled. The rotor can be used also to perform the same reaction in all the vessels.
8) WHEN IT IS POSSIBLE TO OPEN THE REACTOR Before opening the vessel, its always better to wait at least until the temperature is 10C below the boiling point of the solvent to be sure there isnt any pressure inside the vessel. It is recommended to open the reactor slowly under a fume hood.
9) WHAT TO DO WHEN AN EXOTHERMY IS PRESENT If a very fast increase of temperature is noticed during the ramp-step of the reaction (80-100C/min), immediately stop the microwave program. Probably one reagent is highly reactive and the efficient microwave heating creates a large exothermic effect in the reaction. For example, a big exothermic effect (100C in less than minute) has been observed in the alkylation of a primary ammine. No problem is observed with secondary or tertiary ammine.
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Also, the presence of a salt in a solution (for example salt plus water) has shown a large reactivity with microwave. In this case, it is better to use: - a small amount of salt (to have a small ionic conduction effect) - a small quantity of power - long heating ramp.
10) IS IT POSSIBLE TO USE MICROWAVE AT CONSTANT POWER A microwave program at constant power can be used, but only with an open system. In this case the maximum temperature that can be reached is the boiling point of the solvent. The two parameters that need to be fixed are: time and power. Constant power is not recommended in closed vessels because the temperature can rise without limit, and the vessels can be damaged.
11) HOW TO PERFORM SOLID STATE REACTION In the case of solid state reaction, two situations can be considered: a) reagent absorption on solid support (as silice or alumina) b) reaction between neat reagent (liquid-liquid, liquid-solid) a) reagents absorption on solid support: in this case a very efficient stirring is needed. Magnetic stirring is not enough, and mechanical stirring is required in order to have an homogeneous heating of the solid and to be sure that no hot spots are present in the mixture. In this case, a specific modification of the labstation is required to have a more efficient stirring b) reaction between neat reagents: here, three cases can be distinguished: the two reagents are liquid: proceed as standard reaction with solvent For example, the synthesis of the ionic liquid 1-Butyl-3methylimidazolium chloride is run between neat reagents under microwave irradiation. Both reagents, the butyl chloride (bp = 77C) and the 1- methylimidazole (bp = 198C), are liquid at room temperature.
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Me N
+ BuCl
Me N
Bu +
Cl-
Synthesis of 1-butyl-3-methylimidazolium chloride
one reagent is liquid (in large quantity as a solvent), one is solid: presence of heterogeneous mixture, use a good magnetic stirring and proceed as a standard reaction in an open or closed system For example, in the hydrolysis of benzamide, one reagent (benzamide) is solid, the other one, the 20% sulfuric acid, is a liquid present in large quantity (ratio benzamide/sulfuric acid: 100 mg benzamide/ml sulfuric acid)
O NH2 20% H2SO4 O OH
Hydrolysis of benzamide
the two reagents are solid: two cases can be considered: the two solid reagents are melted during the heating: if the quantity is small (up to 5-10 grams), the reaction can be run with standard magnetic stirring. if quantity is large, a specific stirring system is required (see chapter 11, point a). For example, in the synthesis of 4,5-diphenyl-4imidazolin-2-one,
OH NH2 + O O NH2 N N
Condensation of benzoine and urea
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the two reagents (benzoin and urea) have a melting point of 130C. The reaction is usually performed at 150C. At this temperature both the reagents are liquid and the reaction can be run under standard conditions.
the two solid reagents remain solid during the reaction: specific stirring system is required (see chapter 11, point a)
12) HOW TO WORK WITH METAL POWDER (HETEROGENEOUS SOLUTION) Metal powders in the reaction mixture can create a spark and source of ignition that it is possible to prevent in a solvent environment. In order to reduce the risk of exothermic reaction, it is recommended: - That the metal powders always be completely submerged in the solvent and that the vessel be purged with inert gas (Nitrogen, Argon) before closing. - Good stirring of the mixture is needed to ensure a homogeneous distribution of the powders. - Use the minimum amount of catalyst. - Make sure when using the 100 mL/ 270 mL/ or PRO 16/24 TFM reactors, that all the reaction solids (catalyst, etc.) are rinsed down into the solvent pool and do not adhere to the sides of the vessel. Catalyst sticking to the side of the vessel wall can absorb microwave energy excessively, resulting in vessel melt down. - Never use metal without solvent.
13) MAXIMUM HEATING TIME To avoid overheating the reactor, the maximum heating time for a reaction is one hour. If a longer reaction time is needed, repeat the same program more times for one hour.
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14) WHICH CHEMISTRY IS NOT SUITABLE FOR MICROWAVE Reactions that are extremely exothermic should not be performed in the instrument. Hydrogen peroxide is, for example, not suitable to use at high temperature, regardless of the technique, because it is explosive. When working with reaction mixtures that contain large amounts of ions or that can release gases, extra precaution is advisable since the heating rate might be very high and the pressure increase may be correspondingly quick due to the closed vessel system. In this case, the experiment can be performed at low concentration (very diluted solution).
Ionic liquids are often used as an alternative for organic solvent or as a co-solvent for microwave transparent (non polar) reaction mixtures. Ionic liquids are environmentally friendly, recyclable alternatives to dipolar solvents. Their dielectric properties make then highly suitable for use as solvents or additives as they absorb microwaves efficiently. Consequently, their heating rate is very high and the temperature rises very quickly. Therefore, to avoid an exothermic reaction, it is recommended to use a small amount of the ionic liquid. The recommended ratio is 0.2 mmol of ionic liquid/ 2 ml of solvent. Example: 1-butyl-3-methylimidazolium hexafluorophosphate:
Me N
Bu + PF6-
PM = 284.2 and density 1.37 g/ml 0.2 mmol correspond to 56 mg of reagent and in term of volume is 41 l, or 0.04 ml. The ratio solvent: ionic liquid is: 2:0.04 = 50. The amount of ionic liquid needed to heat up the solvent is very small but sufficient and ensures safety when working with them.
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LIST OF THE COMMON SOLVENTS USED Solvent Name (+)-Camphor (Trifluoromethyl)benzene 1,1,2,2-Tetrabromoethane 1,1,2,2-Tetrachloro-1,2-d 1,1,2-Trichloroethane 1,1,2-Trichlorofluoroetha 1,1-Dichloroethane 1,1-Dichloroethylene 1,1-Difluoroethane 1,2,3,4-Tetrahydronaphtha 1,2,3-Trichloropropane 1,2-Dibromoethane 1,2-Dibromopropane 1,2-Dibromotetrafluoroeth 1,2-Dichloroethane 1,2-Dichlorotetrafluoroet 1,2-Epoxybutane 1,2-Propanediol 1,3-Butanediol 1,3-Propanediol 1,4-Dioxane 1,5-Pentanediol 1-Bromobutane 1-Bromonaphthalene 1-Bromopentane 1-Bromopropane Boiling Point [C] 207,4 102,1 243,5 92,8 113,8 47,7 57,4 31,6 -24,9 207,6 157 131,6 141,9 47,3 83,5 3,8 63,3 187,6 207,5 214,4 101,5 239 101,6 281 129,8 71,1 dH evap [KJ/mol] 59,5 32,6 48,7 35 34,8 27 28,9 26,1 21,6 43,9 37,1 34,8 35,6 27 32 23,3 30,3 52,4 58,5 57,9 34,2 60,7 32,5 39,3 35 29,8
Basic Guidelines for Microwave Organic Chemistry Application Rev. 0/04 April 2004 Milestone Srl
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Solvent Name 1-Butanethiol 1-Butanol 1-Chloro-2-methylpropane 1-Chloro-3-methylbutane 1-Chlorobutane 1-Chloronaphthalene 1-Chloropentane 1-Chloropropane 1-Decene 1-Dodecene 1-Hexanol 1-Hexene 1-Iodo-2-methylpropane 1-Iodobutane 1-Iodopropane 1-Methylcyclohexanol 1-Methylnaphthalene 1-Nitropropane 1-Octanol 1-Octene 1-Pentanol 1-Pentene 1-Propanol 2,2,3-Trimethylbutane 2,2,3-Trimethylpentane 2,2,4,4-Tetramethylpentan 2,2,4-Trimethylpentane 2,2,5-Trimethylhexane
Boiling Point [C] 98,5 117,7 68,5 98,9 78,6 259 107,8 46,5 170,5 213,8 157,6 63,4 121,1 130,6 102,6 155 244,7 131,1 195,1 121,2 137,9 29,2 97,2 80,8 110 122,2 99,2 124
dH evap [KJ/mol] 32,2 43,3 29,2 32 30,4 52,1 33,2 27,2 38,7 44 44,5 28,3 33,5 34,7 32,1 79 45,5 38,5 46,9 34,1 44,4 25,2 41,4 28,9 31,9 32,5 30,8 33,7
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Solvent Name 2,2-Dimethylbutane 2,2-Dimethylhexane 2,2-Dimethylpentane 2,3,3-Trimethylpentane 2,3,5-Trimethylhexane 2,3-Dimethylbutane 2,3-Dimethylpentane 2,4,6-Trimethylpyridine 2,4-Dimethylpentane 2,4-Lutidine 2,4-Xylenol 2,5-Xylenol 2,6-Lutidine 2,6-Xylenol 2-Bromo-2-methylpropane 2-Bromobutane 2-Bromopropane 2-Butanol 2-Chloro-2-methylpropane 2-Chlorobutane 2-Chloropropane 2-Ethyl-1-butanol 2-Ethyl-1-hexanol 2-Ethylhexyl acetate 2-Ethylhexylamine 2-Hexanol 2-Iodobutane 2-Iodopropane
Boiling Point [C] 49,7 106,8 79,2 114,8 131,4 57,9 89,7 170,6 80,4 158,5 210,9 211,1 144,1 201 73,3 91,2 59,5 99,5 50,9 68,2 35,7 147 184,6 199 169,2 140 120 89,5
dH evap [KJ/mol] 26,3 32,1 29,2 32,1 34,4 27,4 30,5 39,9 29,6 38,5 47,1 46,9 37,5 44,5 29,2 30,8 28,3 40,8 27,6 29,2 26,3 43,2 54,2 43,5 40 41 33,3 30,7
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Solvent Name 2-Methyl-1-butanol 2-Methyl-1-pentanol 2-Methyl-1-propanol 2-Methyl-2-butanol 2-Methyl-2-pentanol 2-Methyl-2-propanol 2-Methylheptane 2-Methylhexane 2-Methylpentane 2-Methylpropanenitrile 2-Methylthiophene 2-Nitropropane 2-Octanol 2-Pentanol 2-Picoline 2-Propanol 3,3-Diethylpentane 3,3-Dimethylhexane 3,3-Dimethylpentane 3,4-Dimethylhexane 3,4-Xylenol 3,5-Xylenol 3-Ethyl-2-methylpentane 3-Ethyl-3-methylpentane 3-Ethylhexane 3-Ethylpentane 3-Heptanol 3-Methyl-1-butanol
Boiling Point [C] 128 149 107,8 102,4 121,1 82,4 117,6 90 60,2 103,9 12,6 120,2 180 119,3 129,3 82,3 146,3 111,9 86 117,7 227 221,7 115,6 118,2 118,6 93,5 157 131,1
dH evap [KJ/mol] 45,2 50,2 41,8 39 39,6 39,1 33,3 30,6 27,8 32,4 33,9 36,8 44,4 41,4 36,2 39,9 34,6 32,3 29,6 33,2 49,7 49,3 32,9 32,8 33,6 31,1 42,5 44,1
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Solvent Name 3-Methyl-2-butanol 3-Methylheptane 3-Methylhexane 3-Methylpentane 3-Methylthiophene 3-Pentanol 3-Picoline 4-Methyl-2-pentanol 4-Methylheptane 4-Picoline Acetal Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetonphenone Acetylacetone Acrolein Acrylonitrile Allyl acetate Allyl alcohol Aniline Anisole Benzaldehyde Benzene Benzenethiol Benzonitrile
Boiling Point [C] 112,9 116,5 92 63,2 115,5 116,2 144,1 131,6 117,7 145,3 102,2 20,1 117,9 139,5 56 81,6 202 138 52,6 77,3 103,5 97 184,1 153,7 179 80 169,1 191,1
dH evap [KJ/mol] 41,8 33,7 30,9 28,1 34,2 43,5 37,4 44,2 33,4 37,5 36,3 25,8 23,7 38,2 29,1 29,8 38,8 34,3 28,3 32,6 36,3 40 42,4 39 42,5 30,7 39,9 45,9
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Solvent Name Benzyl acetate Benzyl alcohol Benzyl benzoate Bis(2-chloroethyl) ether Bromochloromethane Bromoethane Bromoethylene Bromomethane Butanal Butane Butanenitrile Butanoic anhydride Butyl acetate Butyl ethyl ether Butyl formate Butyl methyl ketone Butyl vinyl ether Butylamine Butylbenzene Butyrolactone Carbon disulfide Chlorobenzene Chlorodifluoromethane Chloroethane Chloroethylene Chloromethane Chloropentafluoroethane Chlorotrifluoromethane
Boiling Point [C] 213 205,3 323,5 178,5 68 38,5 15,8 3,5 74,8 -0,5 117,6 200 126,1 92,3 106,1 127,6 94 77 183,3 204 46 131,7 -40,7 12,3 -13,3 -24 -37,9 -81,4
dH evap [KJ/mol] 49,4 50,5 53,6 45,2 30 27 23,4 23,9 31,5 22,4 33,7 50 36,3 31,6 36,6 36,4 31,6 31,8 38,9 52,2 26,7 35,2 20,2 24,7 20,8 21,4 19,4 15,8
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Solvent Name cis-1,2-Dichloroethylene
Boiling Point [C] 60,1 129,8 36,9 195,8 152,4 80,7 155,4 82,9 134 49,3 130,5 174,1 97 140,2 340 185 159,6 -29,8 8,9 40 268,8 126 34,5 101,9 200 185,7 92,1 55,5
dH evap [KJ/mol] 30,2 33,5 26,1 41 37,5 30 40,3 30,5 36,1 27,3 36,4 38,8 32,9 36,5 79,2 41,3 38,4 20,1 25,2 28,1 65,2 36,2 26,5 33,5 54,8 42 31,8 29,1
cis-1,2-Dimethylcyclohexa cis-2-Pentene cis-Decahydronaphthalene Cumene Cyclohexane Cyclohexanone Cyclohexene Cyclohexylamine Cyclopentane Cyclopentanone Decane Dibromomethane Dibutyl ether Dibutyl phthalate Dibutyl sulfide Dibutylamine Dichlorodifluoromethyane Dichlorofluoromethane Dichloromethane Diethanolamine Diethyl carbonate Diethyl ether Diethyl ketone Diethyl malonate Diethyl oxalate Diethyl sulfide Diethylamine
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Solvent Name Diethylene glycol Diethylene glycol diethyl Diiodomethane Diisobutyl ketone Diisopentyl ether Diisopropyl ether Diisopropyl ketone Diisopropylamine Dimethyl disulfide Dimethyl ether Dimethyl sulfide Dimethyl sulfoxide Dimethylamine Diphenyl ether Dipropyl ether Dipropylamine Dodecane Ethanol Ethanolamine Ethyl acetate Ethyl acrylate Ethyl butanoate Ethyl formate Ethyl isovalerate Ethyl propanoate Ethyl vinyl ether Ethylbenzene Ethylcyclohexane
Boiling Point [C] 245,8 188 182 169,4 172,5 68,5 125,4 83,9 109,8 -24,8 37,3 189 6,8 258 90 109,3 216,3 78,2 171 77,1 99,4 121,5 54,4 135 99,1 35,5 136,1 131,9
dH evap [KJ/mol] 52,3 49 42,5 39,9 35,1 29,1 34,6 30,4 33,8 21,5 27 43,1 26,4 48,2 31,3 33,5 44,5 38,6 49,8 31,9 34,7 35,5 29,9 37 33,9 26,2 35,6 34
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Solvent Name Ethylene glycol Ethylene glycol diacetate Ethylene glycol diethyl e Ethylene glycol dimethyl
Boiling Point [C] 197,3 190 119,4 85 143 84,7 101 31,5 161,7 171 290 98,5 80,2 68,7 197,1 188,4 72,5 42,5 -11,7 116,5 98,2 148,6 67,7 172,7 27,8 142,5 190,4 88,6
dH evap [KJ/mol] 50,5 45,5 36,3 32,4 43,9 31,2 22,7 27,1 43,2 53,6 61 31,8 31,7 28,9 57,3 39,5 29,4 27,3 21,3 35,9 33,6 38,2 30,6 37,8 24,7 37,5 45,9 32,9
Ethylene glycol monoethyl Fluorobenzene Formic acid Furan Furfural Furfuryl alcohol Glycerol Heptane Hexafluorobenzene Hexane Hexylene glycol Iodobenzene Iodoethane Iodomethane Isobutane Isobutyl acetate Isobutyl formate Isobutyl isobutanoate Isobutylamine Isobutylbenzene Isopentane Isopentyl acetate Isopentyl isopentanoate Isopropyl acetate
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Solvent Name Isopropylamine Isoquinoline m-Cresol m-Dichlorobenzene m-Toluidine m-Xylene Mesityl oxide Mesitylene Methanol Methyl acetate Methyl acrylate Methyl ethyl ketone Methyl formate Methyl isobutyl ketone Methyl pentyl ketone Methyl propyl ketone Methyl salicylate Methylacrylonitrile Methylamine Methylcyanoacetate Methylcyclohexane Methylcyclopentane Methylmethycrylate Morpholine N,N-Dimethylacetamide N,N-Dimethylformamide Naphtalene Neopentane
Boiling Point [C] 31,7 243,2 202,2 173 203,3 139,1 130 164,7 64,6 56,8 80,7 79,5 31,7 116,5 151 102,2 222,9 90,3 -6,3 200,5 100,9 71,8 100,5 128 165 153 217,9 9,4
dH evap [KJ/mol] 27,8 49 47,4 38,6 44,9 35,7 36,1 39 35,2 30,3 33,1 31,3 27,9 34,5 38,3 33,4 46,7 31,8 25,6 48,2 31,3 29,1 36 37,1 43,4 38,4 43,2 22,7
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Solvent Name Nitroethane Nitromethane Nonane o-Chloraniline o-Chlorotoluene o-Cresol o-Dichlorobenzene o-Fluorotoluene o-Toluidine o-Xylene Octane Octanoic acid Oleic acid p-Chlorotoluene p-Cresol p-Cymene p-Dichlorobenzene p-Fluorotoluene p-Toluidine p-Xylene Pentachloroethane Pentane Pentanenitrile Pentanoic acid Pentyl acetate Pentylamine Perfuorobutane Perfuorocyclobutane
Boiling Point [C] 114 101,1 150,8 208,8 159 191 180 115 200,3 144,5 125,6 239 360 162,4 201,9 177,1 174 116,6 200,4 138,3 159,8 36 141,3 186,1 149,2 104,3 -1,9 -5,9
dH evap [KJ/mol] 38 34 36,9 44,4 37,5 45,2 39,7 35,4 44,6 36,2 34,4 58,5 67,4 38,7 47,5 38,2 38,8 34,1 44,3 35,7 36,9 25,8 36,1 44,1 41 34 22,9 23,2
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Solvent Name Phenetole Phenol Propanal Propane Propanenitrile Propanoic acid Propanoic anhydride Propyl acetate Propyl formate Propylamine Pyridine Pyrrole Pyrrolidine Quinoline Salicylaldehyde sec-Butylamine Styrene Succinonitrile tert-Butylamine Tetrachloroethylene Tetrachloromethane Tetrahydrofuran Tetrahydrofurfuryl alcoho Tetrahydropyran Tetrahydrothiophene Thiophene Toluene trans-1,2-Dichloroethylen
Boiling Point [C] 169,8 181,8 48 -42,1 97,1 141,1 170 101,5 80,9 47,2 115,2 129,7 86,5 237,1 197 63,5 145 266 44 121,3 76,8 65 178 88 121 84 110,6 48,7
dH evap [KJ/mol] 40,7 45,7 28,3 19 31,8 32,3 41,7 33,9 33,6 29,6 35,1 38,8 33 49,7 38,2 29,9 38,7 48,5 28,3 34,7 29,8 29,8 45,2 31,2 34,7 31,5 33,2 28,9
Page 26
Solvent Name
Boiling Point [C] 123,5 167,5 36,3 187,3 259 149,1 234 216,5 87,2 23,7 61,1 235,4 89 285 73 2,8 178 72,5 100
dH evap [KJ/mol] 33 53 26,1 40,2 57,8 39,7 56,1 46,9 31,4 25,1 29,2 45,7 31 71,4 33,3 22,9 46,4 34,6 40,23
trans-1,2-Dimethylcyclohe trans-2-Methylcyclohexano trans-2-Pentene trans-Decahydronaphthalen Triacetin Tribromomethane Tributyl borate Tributylamine Trichloroethylene Trichlorofluoromethane Trichloromethane Tridecane Triethylamine Triethylene glycol Trifluoroacetic acid Trimethylamine Trinonafluorobutylamine Vinyl acetate Water
Page 27
GRAPHICS OF THE COMMON SOLVENTS USED
Page
Solvent
30 30 31 31 32 32 33 33 34 34 35 35 36 36 37 37 38 38 39 39 40 40 41 41 42 42 43 43
1-Butanol 1-Hexanol 1-Propanol 2-Butanol 2-Hexanol 2-Propanol Acetone Acetylacetone Benzaldehyde Butyl acetate Chlorobenzene Cyclohexane Cyclohexene Dibuthyl ether Dibuthylamine Dichloromethane Diethyl ether Ethanol Ethyl acetate Heptane Hexane Isobuthyl acetate Methanol Methyl ethyl ketone Tetrahydrofuran Toluene Trichloromethane Water
Page 28 Basic Guidelines for Microwave Organic Chemistry Application Rev. 0/04 Milestone Srl
1-Butanol
1-Hexanol
1-Propanol
1-Butanol
2-Hexanol
2-Propanol
Acetone
Acetylacetone
Benzaldehyde
Butyl acetate
Chlorobenzene
Cyclohexane
Cyclohexene
Dibuthyl ether
Dibuthylamine
Dichloromethane
Diethyl ether
Ethanol
Ethyl acetate
Heptane
Hexane
Isobuthyl acetate
Methanol
Methyl ethyl ketone
Tetrahydrofuran
Toluene
Trichloromethane
Water

Basic Guidelines For Microwave Reactor and Reactions

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Basic Guidelines for Microwave Organic Chemistry Applications

UNI EN ISO 9001:2000 Vision certified

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Step1 Step2 Step3 Step4

Below is the temperature profile of 20 mL of Toluene

600 500 400 300

0 00:05:00 00:10:00 00:15:00 00:20:00 00:25:00 00:30:00

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

For example, if the Heck reaction is considered:

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Synthesis of 1-butyl-3-methylimidazolium chloride

Condensation of benzoine and urea

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Solvent Name cis-1,2-Dichloroethylene

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

GRAPHICS OF THE COMMON SOLVENTS USED

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

Methyl ethyl ketone

Basic Guidelines for Microwave Organic Chemistry Application

Basic Guidelines for Microwave Organic Chemistry Application

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