US2302321A - Process for the production of the - Google Patents
Process for the production of the Download PDFInfo
- Publication number
- US2302321A US2302321A US2302321DA US2302321A US 2302321 A US2302321 A US 2302321A US 2302321D A US2302321D A US 2302321DA US 2302321 A US2302321 A US 2302321A
- Authority
- US
- United States
- Prior art keywords
- dilactone
- parts
- acid
- ketopimelic
- organic solvent
- 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
- 238000000034 method Methods 0.000 title description 18
- 238000004519 manufacturing process Methods 0.000 title description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 32
- 239000002253 acid Substances 0.000 description 20
- 239000001384 succinic acid Substances 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 14
- QWUWMCYKGHVNAV-UHFFFAOYSA-N Bibenzyl Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012442 inert solvent Substances 0.000 description 6
- 229940014800 succinic anhydride Drugs 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-Chloronaphthalene Chemical class C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HABHUTWTLGRDDU-UHFFFAOYSA-N 2-oxopimelic acid Chemical compound OC(=O)CCCCC(=O)C(O)=O HABHUTWTLGRDDU-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N Fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000911 decarboxylating Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
Definitions
- the present invention relates to a process for the production of the dilactone of 'y-ketopimelic acid.
- 'y-ketopimelic acid dilactone as is known, can be prepared by decarboxylating dry succinic acid at high temperatures.
- the yield of y-ketopimelic acid dilactone thus obtained does not exceed from 40 to 45 per cent of the theory, because of considerable quantities of unavailable resins and tarry materials being formed simultaneously.
- Suitable inert solvents are, for example, the alkylnaphthalenes, the chloronaphthalenes, fluorene, dibenzyl or high-boiling mineral oils.
- the reaction is carried out by heating the succinic acid or its anhydride, together with an equal or larger or smaller amount of the inert solvent, to a temperature of from 240 to 250 C., if necessary while stirring.
- the quantity of the solvent need not be proportionately increased, since the dilactone formed will act as a solvent.
- the dilactone of the 'y-ketopimelic acid formed is isolated by blowing off the inert solvent, for example, by means of steam or by distillation at normal or reduced pressure, and subsequently subjecting the remaining dilactone to a high vacuum distillation. It boils at 170 C. at a pressure of 2 millimeters (mercury gauge).
- Example 1 90 parts of succinic acid and 150 parts of ozmethylnaphthalene are heated at from 240 to 250 C., while stirring, until carbon dioxide is no longer evolved. After blowing off the a-methylnaphthalene by means of steam, the residue is subjected to a high vacuum distillation. There are obtained 32 parts of 'y-ketopimelic acid dilactone in the form of an almost colorless crystal mass which, being recrystallized from alcohol, melts at 71 C. 17 parts of succinic anhydride are recovered.
- Example 2 90 parts of succinic acid and 30 parts of achloronaphthalene are heated at from 240 to 250 C. until the evolution of carbon dioxide is finished. The a-chloronaphthalene and the unconverted succinic anhydride are then removed by distillation and the dilactone remaining behind is purified by high vacuum distillation. There are obtained 28 parts of 'y-ketopimelic acid dilactone, while from 15 to 20 parts of succinic anhydride are recovered.
- Example 3 parts of succinic acid and 40 parts of dibenzyl are heated at from 240 to 250 C., until carbon dioxide is no longer evolved.
- carbon dioxide is no longer evolved.
- dibenzyl a, mineral oil fraction boiling between 250 and 270 C. may be employed.
- a process for producing 'y-ketopimelic acid dilactone which comprises heating a member of the group consisting of succinic acid and its anhydride to a temperature of between 240 and 250 C. in the presence of an inert organic solvent having a boiling point of at least 240 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Description
Patented Nov. 17, 1942 PROCESS FOR THE PRODUCTION OF THE DILACTONE OF 7 KETOPIMELIC ACID Heinrich Hopfl and Herbert Griesshaber, Ludwigshafen-on-the-Rhine, Germany; vested in the Alien Property Custodian No Drawing. Application June 12, 1941, Serial No. 397,740. In Germany July 8, 1940 6 Claims.
The present invention relates to a process for the production of the dilactone of 'y-ketopimelic acid.
'y-ketopimelic acid dilactone, as is known, can be prepared by decarboxylating dry succinic acid at high temperatures. The yield of y-ketopimelic acid dilactone thus obtained, however, does not exceed from 40 to 45 per cent of the theory, because of considerable quantities of unavailable resins and tarry materials being formed simultaneously.
We have now found that -ketopimelic acid dilactone can be produced with a far better yield by heating succinic acid or its anhydride to a temperature of between 240 and 250 C. in the presence of an inert organic solvent boiling at or above the reacting temperature, i. e. at least at 240 C. A yield of 'y-ketopimelic acid dilactone amounting to 70 per cent and more is obtained in this manner.
Suitable inert solvents are, for example, the alkylnaphthalenes, the chloronaphthalenes, fluorene, dibenzyl or high-boiling mineral oils.
The reaction is carried out by heating the succinic acid or its anhydride, together with an equal or larger or smaller amount of the inert solvent, to a temperature of from 240 to 250 C., if necessary while stirring. When larger quantities of succinic acid are employed, the quantity of the solvent need not be proportionately increased, since the dilactone formed will act as a solvent. The dilactone of the 'y-ketopimelic acid formed is isolated by blowing off the inert solvent, for example, by means of steam or by distillation at normal or reduced pressure, and subsequently subjecting the remaining dilactone to a high vacuum distillation. It boils at 170 C. at a pressure of 2 millimeters (mercury gauge).
The following examples serve to illustrate how the present invention may be carried out in practice, but the invention is not restricted to the said examples. The parts are by weight.
Example 1 90 parts of succinic acid and 150 parts of ozmethylnaphthalene are heated at from 240 to 250 C., while stirring, until carbon dioxide is no longer evolved. After blowing off the a-methylnaphthalene by means of steam, the residue is subjected to a high vacuum distillation. There are obtained 32 parts of 'y-ketopimelic acid dilactone in the form of an almost colorless crystal mass which, being recrystallized from alcohol, melts at 71 C. 17 parts of succinic anhydride are recovered.
Example 2 90 parts of succinic acid and 30 parts of achloronaphthalene are heated at from 240 to 250 C. until the evolution of carbon dioxide is finished. The a-chloronaphthalene and the unconverted succinic anhydride are then removed by distillation and the dilactone remaining behind is purified by high vacuum distillation. There are obtained 28 parts of 'y-ketopimelic acid dilactone, while from 15 to 20 parts of succinic anhydride are recovered.
Example 3 parts of succinic acid and 40 parts of dibenzyl are heated at from 240 to 250 C., until carbon dioxide is no longer evolved. By working up the reaction product in the manner described in Example 2 there are obtained more than 50 per cent (of the theory) of -ketopimelic acid dilactone. Instead of dibenzyl, a, mineral oil fraction boiling between 250 and 270 C. may be employed.
What we claim is:
l. A process for producing 'y-ketopimelic acid dilactone which comprises heating a member of the group consisting of succinic acid and its anhydride to a temperature of between 240 and 250 C. in the presence of an inert organic solvent having a boiling point of at least 240 C.
-2. The process as described in claim 1, Wherein the inert organic solvent as defined therein is an alkylnaphthalene.
3. The process as described in claim 1, wherein the inert organic solvent is a-methylnaphthalene.
4. The process as described in claim 1, wherein the inert organic solvent as defined therein is a chloronaphthalene.
5. The process as described in claim 1, wherein the inert organic solvent is u-chloronaphthalene.
6. The process as described in claim 1, wherein the inert organic solvent is dibenzyl.
HEINRICH HOPFF. HERBERT GRIESSHABER.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2302321A true US2302321A (en) | 1942-11-17 |
Family
ID=3432973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2302321D Expired - Lifetime US2302321A (en) | Process for the production of the |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2302321A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2840570A (en) * | 1955-11-25 | 1958-06-24 | Du Pont | Dilactones and their preparation from carbon monoxide and acetylenes |
| WO2016131004A1 (en) * | 2015-02-13 | 2016-08-18 | Novomer, Inc. | Integrated methods for chemical synthesis |
| US10099988B2 (en) | 2015-02-13 | 2018-10-16 | Novomer, Inc. | Process for production of acrylic acid |
| US10099989B2 (en) | 2015-02-13 | 2018-10-16 | Novomer, Inc. | Distillation process for production of acrylic acid |
| US10221278B2 (en) | 2011-05-13 | 2019-03-05 | Novomer, Inc. | Catalytic carbonylation catalysts and methods |
| US10221150B2 (en) | 2015-02-13 | 2019-03-05 | Novomer, Inc. | Continuous carbonylation processes |
| US10597294B2 (en) | 2014-05-30 | 2020-03-24 | Novomer, Inc. | Integrated methods for chemical synthesis |
| US10858329B2 (en) | 2014-05-05 | 2020-12-08 | Novomer, Inc. | Catalyst recycle methods |
| US10974234B2 (en) | 2014-07-25 | 2021-04-13 | Novomer, Inc. | Synthesis of metal complexes and uses thereof |
-
0
- US US2302321D patent/US2302321A/en not_active Expired - Lifetime
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2840570A (en) * | 1955-11-25 | 1958-06-24 | Du Pont | Dilactones and their preparation from carbon monoxide and acetylenes |
| US10479861B2 (en) | 2011-05-13 | 2019-11-19 | Novomer, Inc. | Catalytic carbonylation catalysts and methods |
| US10221278B2 (en) | 2011-05-13 | 2019-03-05 | Novomer, Inc. | Catalytic carbonylation catalysts and methods |
| US11667617B2 (en) | 2014-05-05 | 2023-06-06 | Novomer, Inc. | Catalyst recycle methods |
| US10858329B2 (en) | 2014-05-05 | 2020-12-08 | Novomer, Inc. | Catalyst recycle methods |
| US10829372B2 (en) | 2014-05-30 | 2020-11-10 | Novomer, Inc. | Integrated methods for chemical synthesis |
| US10597294B2 (en) | 2014-05-30 | 2020-03-24 | Novomer, Inc. | Integrated methods for chemical synthesis |
| US10974234B2 (en) | 2014-07-25 | 2021-04-13 | Novomer, Inc. | Synthesis of metal complexes and uses thereof |
| US10221150B2 (en) | 2015-02-13 | 2019-03-05 | Novomer, Inc. | Continuous carbonylation processes |
| US10626073B2 (en) | 2015-02-13 | 2020-04-21 | Novomer, Inc. | Process for production of acrylic acid |
| US10717695B2 (en) | 2015-02-13 | 2020-07-21 | Novomer, Inc. | Distillation process for production of acrylic acid |
| US10738022B2 (en) | 2015-02-13 | 2020-08-11 | Novomer, Inc. | Continuous carbonylation processes |
| US10099989B2 (en) | 2015-02-13 | 2018-10-16 | Novomer, Inc. | Distillation process for production of acrylic acid |
| US10099988B2 (en) | 2015-02-13 | 2018-10-16 | Novomer, Inc. | Process for production of acrylic acid |
| US10927091B2 (en) | 2015-02-13 | 2021-02-23 | Novomer, Inc. | Continuous carbonylation processes |
| JP2018506547A (en) * | 2015-02-13 | 2018-03-08 | ノボマー， インコーポレイテッド | An integrated method for chemical synthesis. |
| US11078172B2 (en) | 2015-02-13 | 2021-08-03 | Novomer, Inc. | Integrated methods for chemical synthesis |
| US11155511B2 (en) | 2015-02-13 | 2021-10-26 | Novomer, Inc. | Distillation process for production of acrylic acid |
| WO2016131004A1 (en) * | 2015-02-13 | 2016-08-18 | Novomer, Inc. | Integrated methods for chemical synthesis |
| US11807613B2 (en) | 2015-02-13 | 2023-11-07 | Novomer, Inc. | Integrated methods for chemical synthesis |
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