CA1283415C - Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140 c and product is isolated by solvent extraction - Google Patents
Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140 c and product is isolated by solvent extractionInfo
- Publication number
- CA1283415C CA1283415C CA000523061A CA523061A CA1283415C CA 1283415 C CA1283415 C CA 1283415C CA 000523061 A CA000523061 A CA 000523061A CA 523061 A CA523061 A CA 523061A CA 1283415 C CA1283415 C CA 1283415C
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- bicyclic amide
- solvent
- amine
- group containing
- 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.)
- Expired - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
An improved process as described for preparing bicyclic amide acetals from an organic nitrile and a dialkanol amine, wherein the reaction temperature is maintained in the range of from room temperature to 140°C. The resulting bicyclic amide acetal product is removed from the reaction mixture by extraction into a hydrocarbon or organic nitrile solvent prior to its purification. These acetals were found to be particularly suitable as chemical intermediates in the preparation of polyurethanes, epoxy resins and the like.
An improved process as described for preparing bicyclic amide acetals from an organic nitrile and a dialkanol amine, wherein the reaction temperature is maintained in the range of from room temperature to 140°C. The resulting bicyclic amide acetal product is removed from the reaction mixture by extraction into a hydrocarbon or organic nitrile solvent prior to its purification. These acetals were found to be particularly suitable as chemical intermediates in the preparation of polyurethanes, epoxy resins and the like.
Description
128341~;
AN IMPROVED PROOESS FOR 'l~n~: PREPAR~TION OF
BICYCLIC AMIDE ACETALS
This invention relates to an improved process for the preparation of bicyclic amide acetals by the reaction of an organic nitrile with a dialkanol amine wherein the reaction temperature is maintained below about 140 degrees C. and the bicyclic amide acetal is removed from the reaction mixture by extraction in a hydrocarbon solvent.
The synthesis of bicyclic amide acetals by the reaction of a dialkanol amine, such as diethanol amine with alkyl nitriles has been reported to result in relatively low yields (30-40%) in Agnew_Chem. 85, Patenk Publication No. 2,344,607.
Reaction temperatures used in this synthesis have been in the range of 120 to 180C. The preparation and reactions of bicyclic amide acetals are also described in Synthesis, (1~71), pp. 16-26.
Although low yield synthesis of bicyclic amide acetals by the reaction of dialkanol amines and nitriles at 120 to 180 degrees C., usually in the presence of a catalyst such as an alkali metal, has been described, no reaction between the dialkanol amine and the bicyclic amide acetal at these temperatures has been disclosed. Because all of the bicyclic amide acetals boil at temperatures greater than 170 degrees C.
under ambient pressure, and at these temperatures the dialkanol amine reacts with the bicyclic amide acetal, lower yields in the prior art process were inevitable. The use of solvent extraction to separate the bicyclic amide acetal from the reaction mixture to produce significantly higher yields has not .~ ~
~8~ 5 previously been disclosed or suggested. The extraction solvent can be any inert solvent and can even include an excess of the _ starting nitrile itself.
The bicyclic amide acetals produced by the improved process of this invention include those having the Formula I
~"
~..
, P
~1: ~
/
I
wherein n is 1 or 2, R and R~ independently represent hydrogen, an alkyl group containing from 1 to 10 carbon atoms or an aryl group containing from 6 to 12 carbon atoms, and when n is 1, R' represents an alkyl group containing from 1 to 20 carbon atoms, an aryl group containing from 6 to 12 carbon atom~, or an alkaryl group containing from 7 to 20 carbon atoms, and when n is 2, R' represents an al~ylene group containing from 1 to 18 carbon atoms, an arylene group containing from 6 to 14 carbon atoms or an alkarylene group containing from 7 to 20 carbon ~oms .
We have discovered that higher yields of purified bioyclic amide acetals can be obtained by separating the bicyclic amide acetal via solvent extraction prior to any distillation of the bicyclic amide acetal. Thu~, following the reaction of diethanol amine with an alkyl nitrile at a reaction betwe~n room temperature and 140-C. The reaction mixture in our process is subjected to extraction at about room ~Z83~
temperature to isola'ce the bicyclic amide acetal product. The preferred solvents for the extraction of bicyclic amide acetal from the reaction mixture are hydrocarbons and hydro~arbon ethers containing from 2 to 20 carbon atoms and most preferred are aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether and aromatic hydrocarbons such as benzene and toluene. The starting nitriles themselves can also be used as extraction solvents in our invention. In the extraction the bicyclic amide acetals selectively go into the solvent layer and dialkanol amine and catalyst as well as high boiling byproducts remain in the remainder of the reaction mixture.
The extracted bicyclic amide acetal, along with the nitrile and solvent can then be sub~ected to fractional distillation at any desired temperature without loss of yield. The use of an excess amount of the nitrile often obviates the necessity for any other solvent. The nitrile containing the bicyclic amide acetal separates and can be isolated readily from the remainder of the reaction mixture.
The organic nitriles useful in this process include aliphatic mononitriles having from 1 to 20 carbon atoms, aromatlc mononitriles having from 7 to 15 carbon atoms and alkylaromatic mononitriles having from 8 to 20 carbon atoms and aliphatic dinitriles having from 3 to 22 carbon atoms, aromatic dinitriles having from 8 to 16 carbon atoms and alkaryl dinitriles having from 9 to 21 carbon atoms.
The dialkanol amines useful in the process of this invention include substituted and unsubstituted dialkanol amines having the general formula HOC(R)2CH2NHCH2C(R")20H
wherein R and R" have the foregoing designations.
.~
12~3341~
The process of this invention is further illustrated in the following representative examples.
Diethanol amine (0.26g) and a bicyclic amide acetal of Formula I wherein n is 1, R and R" are hydrogen and R' is benzyl (0.51~ were mixed and heated in a closed mini reactor with constant stirring at 160C. for 2 1/2 hours. GLC analysis of the mixture showed that 47% of the diethanol amine and about 55% of the bicyclic amide acetal had reacted (were no longer present).
~XAMPLE 2 Diethanol amine (1.08g) and a bicyclic amide acetal of Formula I where n is 1, R and R" are hydrogen and R' is methyl (1.3g) were mixed in a mini reactor and heated at 120C. for thrse hours, followed by heating at 150C. for two hours. GLC
analysis of the mixture indicated that about 20% by weight of the starting diethanol amine and 25% of the bicyclic amide acetal had reacted.
Diethanol amine (1.05g) and the bicyclic amide acetal of Formula I in which n is 1, R and R" are hydrogen and Rl' is methyl (1.25g) were mixed and heated at 120C for three hours.
GLC analysis showed the consumption of only about 2% by weight of each reactant.
XANPL~ 4 The procedure of the pxior art (German Patent Publication No. 1,344,~07) was followed using 117.15g of benzyl nitrile and 105.14g of diethanol amine. The reaction was carried out at 140C. for about 20 hours. The GLC analysis of 1283~5 the reaction mixture indicat~d the presence OI about 6 by weight of the product of Formula I wherein n is 1, R
and R" are hydrogen and R' is benzyl and about 10~ by weight of benzyl nitrile and 4% of diethanol amine. The reaction mixture was subjected to fractional distillation under reduced pressure. Because of the high boiling nature of the product, the pot temperature had to be increased about 150C. in order to distill the product at 110-20C.
10 /Or 6-2 mm Hg pressure which afforded a 41% overall yield of the bicyclic amide acetal. The pot residue ~95g, 43%) was found to contain only traces o~ the product bicyclic amide acetal and was highly viscous indicating higher molecular weight byproducts. This shows that about 14% by weight of the bicyclic amide acetal product was lost during the isolation by distillation.
EXAMPLE S
Diethanol amine (25.6g) containing 2 mole percent of sodium and benzonitrile (25g) were mixed and heated at 100C. for 56 hours under nitrogen. The GLC
analysis of the reaction mixture indicated the formation of about 3B% by weight of bicyclic amide acetal of Formula I wherein n is 1, R is 1, R and R"
are hydrogen and R' is phenyl. The reaction mixture was brought back to room temperature and the product and the unreacted benzonitrile were separated from diethanol ami~e and the catalyst by extr~ction with three 40 ml portions of hexane and 20 ml of toluene.
GLC analysis of the com~ined extracts showed them to contain mainly the nitrile and the bicyclic amide acetal product with only traces ~less than 1~) of diethanol amine, whereas the residue was found ts be mainly diethanol amine with traces (1 to 2%) of bicyclic amide ace~al and nitrile. The solvent was removed from the extract and the rPsidue was fractionally distilled gi~ing a 35% yield of the bicyclic amide acetal (78-79~C./0.02 mm Hg~. This , lZ~334~;
experiment demonstrates that essentially no loss of product occurs when separation of product ~y extraction is carried out prior to the distillation step which precludes possible reaction between the bicyclic amide acetal and diethanol amine.
The procedure of Example 5 was repeated using 52,7g of diethanol amine with 2 mole percent of sodium and 90.7g of undecyl nitrile. GLC analysis of the reaction mixture after 72 hours of reaction at 100~ C.
showed the formation of about 42% of the bicyclic ~mide acetal of Eormula I in which n is 1, R and ~ are hydrogen and R' is undecyl. The extraction with pentane (three 50 ml portions) and fractional distillation of the extract afforded about 52g (greater than 3~% yield) of the bicyclic amide acetal product.
A 40g mixture containing approximately 50% by weight of diethanol amine, 45% of a bicyclic amide acetal of Formula I wherein n is 1~ R and R" are hydrogen and R" is methyl and 5% of acetonitrile w~s extracted with three 80 ml por~ions of pentane at room ~5 temperature. The extracts were combined and analyzed and it was found that 95% of the total bicyclic amide acetal had been extracted. The GLC analysis of the residue not extracted showed thP presence mainly of diethanol amine with about 5% of the bicyclic ~mide acetal.
EXA~PLE 8 A mixture of 20% by weight of the bicyclic amide acetal of Example 7 and 80% of diethanol amine. The bicyclic amide acetal was separated by extraction using acetonitrile as the solvent as in Example 7, GLC
.
',,~ ,~,0 ~;283~5 analysis of the residue left after extraction indicated the presence of 95% of diethanol amine and about 5~ of the bicyclic amide acetal.
Acetonitrile (83.8g, 2.04 mols) and diethanol-amine (88.2g, 0.84 mol1 containing 2 mole% of sodium (based on diethanol amine) as catalyst were reacted for 30 hours at 79C. to produce the methyl bicyclic amide acetal of Formula I wherein n is l, R
and R" are hydrogen and R' is methyl in 75% yield.
Separation of the bicyclic amide acetal product from the unreacted starting material and catalyst was accomplished with pentane solvent. The pentane lS extracted 93.5% of the bicyclic amide and no diethanol amine (GLC analysis). The mo~her liquor left after $he extraction was found by GC to contain 100% of the unreacted diethanol amine and only 6.5% of the bicyclic amide acetal.
AN IMPROVED PROOESS FOR 'l~n~: PREPAR~TION OF
BICYCLIC AMIDE ACETALS
This invention relates to an improved process for the preparation of bicyclic amide acetals by the reaction of an organic nitrile with a dialkanol amine wherein the reaction temperature is maintained below about 140 degrees C. and the bicyclic amide acetal is removed from the reaction mixture by extraction in a hydrocarbon solvent.
The synthesis of bicyclic amide acetals by the reaction of a dialkanol amine, such as diethanol amine with alkyl nitriles has been reported to result in relatively low yields (30-40%) in Agnew_Chem. 85, Patenk Publication No. 2,344,607.
Reaction temperatures used in this synthesis have been in the range of 120 to 180C. The preparation and reactions of bicyclic amide acetals are also described in Synthesis, (1~71), pp. 16-26.
Although low yield synthesis of bicyclic amide acetals by the reaction of dialkanol amines and nitriles at 120 to 180 degrees C., usually in the presence of a catalyst such as an alkali metal, has been described, no reaction between the dialkanol amine and the bicyclic amide acetal at these temperatures has been disclosed. Because all of the bicyclic amide acetals boil at temperatures greater than 170 degrees C.
under ambient pressure, and at these temperatures the dialkanol amine reacts with the bicyclic amide acetal, lower yields in the prior art process were inevitable. The use of solvent extraction to separate the bicyclic amide acetal from the reaction mixture to produce significantly higher yields has not .~ ~
~8~ 5 previously been disclosed or suggested. The extraction solvent can be any inert solvent and can even include an excess of the _ starting nitrile itself.
The bicyclic amide acetals produced by the improved process of this invention include those having the Formula I
~"
~..
, P
~1: ~
/
I
wherein n is 1 or 2, R and R~ independently represent hydrogen, an alkyl group containing from 1 to 10 carbon atoms or an aryl group containing from 6 to 12 carbon atoms, and when n is 1, R' represents an alkyl group containing from 1 to 20 carbon atoms, an aryl group containing from 6 to 12 carbon atom~, or an alkaryl group containing from 7 to 20 carbon atoms, and when n is 2, R' represents an al~ylene group containing from 1 to 18 carbon atoms, an arylene group containing from 6 to 14 carbon atoms or an alkarylene group containing from 7 to 20 carbon ~oms .
We have discovered that higher yields of purified bioyclic amide acetals can be obtained by separating the bicyclic amide acetal via solvent extraction prior to any distillation of the bicyclic amide acetal. Thu~, following the reaction of diethanol amine with an alkyl nitrile at a reaction betwe~n room temperature and 140-C. The reaction mixture in our process is subjected to extraction at about room ~Z83~
temperature to isola'ce the bicyclic amide acetal product. The preferred solvents for the extraction of bicyclic amide acetal from the reaction mixture are hydrocarbons and hydro~arbon ethers containing from 2 to 20 carbon atoms and most preferred are aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether and aromatic hydrocarbons such as benzene and toluene. The starting nitriles themselves can also be used as extraction solvents in our invention. In the extraction the bicyclic amide acetals selectively go into the solvent layer and dialkanol amine and catalyst as well as high boiling byproducts remain in the remainder of the reaction mixture.
The extracted bicyclic amide acetal, along with the nitrile and solvent can then be sub~ected to fractional distillation at any desired temperature without loss of yield. The use of an excess amount of the nitrile often obviates the necessity for any other solvent. The nitrile containing the bicyclic amide acetal separates and can be isolated readily from the remainder of the reaction mixture.
The organic nitriles useful in this process include aliphatic mononitriles having from 1 to 20 carbon atoms, aromatlc mononitriles having from 7 to 15 carbon atoms and alkylaromatic mononitriles having from 8 to 20 carbon atoms and aliphatic dinitriles having from 3 to 22 carbon atoms, aromatic dinitriles having from 8 to 16 carbon atoms and alkaryl dinitriles having from 9 to 21 carbon atoms.
The dialkanol amines useful in the process of this invention include substituted and unsubstituted dialkanol amines having the general formula HOC(R)2CH2NHCH2C(R")20H
wherein R and R" have the foregoing designations.
.~
12~3341~
The process of this invention is further illustrated in the following representative examples.
Diethanol amine (0.26g) and a bicyclic amide acetal of Formula I wherein n is 1, R and R" are hydrogen and R' is benzyl (0.51~ were mixed and heated in a closed mini reactor with constant stirring at 160C. for 2 1/2 hours. GLC analysis of the mixture showed that 47% of the diethanol amine and about 55% of the bicyclic amide acetal had reacted (were no longer present).
~XAMPLE 2 Diethanol amine (1.08g) and a bicyclic amide acetal of Formula I where n is 1, R and R" are hydrogen and R' is methyl (1.3g) were mixed in a mini reactor and heated at 120C. for thrse hours, followed by heating at 150C. for two hours. GLC
analysis of the mixture indicated that about 20% by weight of the starting diethanol amine and 25% of the bicyclic amide acetal had reacted.
Diethanol amine (1.05g) and the bicyclic amide acetal of Formula I in which n is 1, R and R" are hydrogen and Rl' is methyl (1.25g) were mixed and heated at 120C for three hours.
GLC analysis showed the consumption of only about 2% by weight of each reactant.
XANPL~ 4 The procedure of the pxior art (German Patent Publication No. 1,344,~07) was followed using 117.15g of benzyl nitrile and 105.14g of diethanol amine. The reaction was carried out at 140C. for about 20 hours. The GLC analysis of 1283~5 the reaction mixture indicat~d the presence OI about 6 by weight of the product of Formula I wherein n is 1, R
and R" are hydrogen and R' is benzyl and about 10~ by weight of benzyl nitrile and 4% of diethanol amine. The reaction mixture was subjected to fractional distillation under reduced pressure. Because of the high boiling nature of the product, the pot temperature had to be increased about 150C. in order to distill the product at 110-20C.
10 /Or 6-2 mm Hg pressure which afforded a 41% overall yield of the bicyclic amide acetal. The pot residue ~95g, 43%) was found to contain only traces o~ the product bicyclic amide acetal and was highly viscous indicating higher molecular weight byproducts. This shows that about 14% by weight of the bicyclic amide acetal product was lost during the isolation by distillation.
EXAMPLE S
Diethanol amine (25.6g) containing 2 mole percent of sodium and benzonitrile (25g) were mixed and heated at 100C. for 56 hours under nitrogen. The GLC
analysis of the reaction mixture indicated the formation of about 3B% by weight of bicyclic amide acetal of Formula I wherein n is 1, R is 1, R and R"
are hydrogen and R' is phenyl. The reaction mixture was brought back to room temperature and the product and the unreacted benzonitrile were separated from diethanol ami~e and the catalyst by extr~ction with three 40 ml portions of hexane and 20 ml of toluene.
GLC analysis of the com~ined extracts showed them to contain mainly the nitrile and the bicyclic amide acetal product with only traces ~less than 1~) of diethanol amine, whereas the residue was found ts be mainly diethanol amine with traces (1 to 2%) of bicyclic amide ace~al and nitrile. The solvent was removed from the extract and the rPsidue was fractionally distilled gi~ing a 35% yield of the bicyclic amide acetal (78-79~C./0.02 mm Hg~. This , lZ~334~;
experiment demonstrates that essentially no loss of product occurs when separation of product ~y extraction is carried out prior to the distillation step which precludes possible reaction between the bicyclic amide acetal and diethanol amine.
The procedure of Example 5 was repeated using 52,7g of diethanol amine with 2 mole percent of sodium and 90.7g of undecyl nitrile. GLC analysis of the reaction mixture after 72 hours of reaction at 100~ C.
showed the formation of about 42% of the bicyclic ~mide acetal of Eormula I in which n is 1, R and ~ are hydrogen and R' is undecyl. The extraction with pentane (three 50 ml portions) and fractional distillation of the extract afforded about 52g (greater than 3~% yield) of the bicyclic amide acetal product.
A 40g mixture containing approximately 50% by weight of diethanol amine, 45% of a bicyclic amide acetal of Formula I wherein n is 1~ R and R" are hydrogen and R" is methyl and 5% of acetonitrile w~s extracted with three 80 ml por~ions of pentane at room ~5 temperature. The extracts were combined and analyzed and it was found that 95% of the total bicyclic amide acetal had been extracted. The GLC analysis of the residue not extracted showed thP presence mainly of diethanol amine with about 5% of the bicyclic ~mide acetal.
EXA~PLE 8 A mixture of 20% by weight of the bicyclic amide acetal of Example 7 and 80% of diethanol amine. The bicyclic amide acetal was separated by extraction using acetonitrile as the solvent as in Example 7, GLC
.
',,~ ,~,0 ~;283~5 analysis of the residue left after extraction indicated the presence of 95% of diethanol amine and about 5~ of the bicyclic amide acetal.
Acetonitrile (83.8g, 2.04 mols) and diethanol-amine (88.2g, 0.84 mol1 containing 2 mole% of sodium (based on diethanol amine) as catalyst were reacted for 30 hours at 79C. to produce the methyl bicyclic amide acetal of Formula I wherein n is l, R
and R" are hydrogen and R' is methyl in 75% yield.
Separation of the bicyclic amide acetal product from the unreacted starting material and catalyst was accomplished with pentane solvent. The pentane lS extracted 93.5% of the bicyclic amide and no diethanol amine (GLC analysis). The mo~her liquor left after $he extraction was found by GC to contain 100% of the unreacted diethanol amine and only 6.5% of the bicyclic amide acetal.
Claims (10)
1. In the process for preparing a bicyclic amide acetal from an organic nitrile and a dialkanol amine the improvement comprising conducting the reaction at a temperature in the range of from room temperature to 140°C. and then extracting the bicyclic amide acetal product from the reaction mixture with a solvent.
2. The process of Claim 1 wherein the bicyclic amide acetal is one conforming to the formula wherein R and R" independently represent hydrogen, an alkyl group containing from 1 to 10 carbon atoms or an aryl group containing from 6 to 12 carbon atoms, and when n is 1, R' represents an alkyl group containing from 1 to 20 carbon atoms, an aryl group containing from 6 to 14 carbon atoms, or an alkaryl group containing from 7 to 20 carbon atoms and when n is 2, R' represents an alkylene group containing from 1 to 18 carbon atoms, an arylene group containing from 6 to 14 carbon atoms or an alkarylene group containing from 7 to 20 carbon atoms.
3. The process of Claim 2 wherein the organic nitrile is one selected from the group consisting of an aliphatic mononitrile having from 1 to 20 carbon atoms, an aromatic mononitrile having from 7 to 15 carbon atoms, an alkaryl mononitrile having from 8 ts 20 carbon atoms, an aliphatic dinitrile having from 3 to 22 carbon atoms, an aromatic dinitrile having from 8 to 16 carbon atoms and an alkaryl dinitrile having from 9 to 21 carbon atoms.
4. The process of Claim 3 wherein the dialkanol amine is one which has the formula HOC(R)2CH2NHCH2C(R")2OH.
5. The process of Claim 4 wherein the solvent is a member selected from the group consisting of the organic nitrile an a hydrocarbon containing from 2 to 20 carbon atoms.
6. The process of Claim 4 wherein the organic nitrile is benzyl nitrile, the dialkanol amine is diethanol amine and the solvent is hexane and toluene.
7. The process of Claim 4 wherein the organic nitrile is undecyl nitrile, the dialkanol amine is diethanol amine and the solvent is pentane.
8. The process of Claim 4 wherein the organic nitrile is acetonitrile, the dialkanol amine is diethanol amine and the solvent pentane and acetonitrile.
9. The process of Claim 4 wherein the organic nitrile is acetonitrile, the dialkanol amine is diethanol amine and the solvent is acetonitrile.
10. The process of Claim 4 wherein the organic nitrile is acetonitrile, the dialkanol amine is diethanol amine and the solvent is pentane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000523061A CA1283415C (en) | 1986-11-14 | 1986-11-14 | Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140 c and product is isolated by solvent extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000523061A CA1283415C (en) | 1986-11-14 | 1986-11-14 | Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140 c and product is isolated by solvent extraction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1283415C true CA1283415C (en) | 1991-04-23 |
Family
ID=4134355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000523061A Expired - Lifetime CA1283415C (en) | 1986-11-14 | 1986-11-14 | Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140 c and product is isolated by solvent extraction |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1283415C (en) |
-
1986
- 1986-11-14 CA CA000523061A patent/CA1283415C/en not_active Expired - Lifetime
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB1560549A (en) | Manufacture of n-substituted glycinonitriles and amino acid salts | |
| CA1283415C (en) | Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140 c and product is isolated by solvent extraction | |
| US4652655A (en) | Bicyclic amide acetals are prepared from organic nitriles and dialkanol amines at below about 140° C. and product is isolated by solvent extraction | |
| EP0449297B1 (en) | Cyanobutylation of amines with 2-pentenenitrile | |
| Lindström et al. | A stereospecific synthesis of vicinal amino alcohols by aminolysis of vinylepoxides | |
| US4719309A (en) | Preparation of imidazoles | |
| US3426072A (en) | Preparation of amine ethers | |
| EP0267976B1 (en) | An improved process for the preparation of bicyclic amide acetals | |
| EP0125726B2 (en) | Improved process for preparing alkyl isocyanates | |
| EP0253354B1 (en) | Monohalogenotrifluorooxetane and its preparation | |
| Brace | Amides as nucleophiles: reaction of alkyl halides with amides or with amides and water. A new look at an old reaction | |
| CA1249590A (en) | Bicyclic amide acetal production | |
| US20230103096A1 (en) | Branched organosilanol compounds and methods for the preparation and use thereof | |
| US3708515A (en) | Process of preparing gamma-cyanobutyraldimines | |
| JPH0422914B2 (en) | ||
| FR2521564A1 (en) | SILANE COMPOUNDS USEFUL AS GLASS ENSIMAGING AGENTS OR AS ADHERENCE PROMOTERS | |
| US4079086A (en) | Process for reacting alkyl epoxides with glycols | |
| US5126476A (en) | Process for the preparation of aryl-, heteroaryl-, or cycloalkyl-substituted alkyl urethanes and isocyanates | |
| US4376861A (en) | Method for preparing 2-alkenyl-2-oxazolines | |
| US4418201A (en) | Process for preparation of N-heterocyclic compounds | |
| CA1148173A (en) | Preparation of aromatic azomethines | |
| CA1174686A (en) | Method for the production of alkyl and alkoxyalkyl substituted benzene compounds | |
| US4822946A (en) | Preparation of olefins from tertiary alkyl halides | |
| JP7111304B2 (en) | Method for producing methylsuccinonitrile or succinonitrile | |
| US4381265A (en) | Aromatic nitrile-containing compounds useful as dyestuff intermediates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |