CS242218B1 - Method of alpha-bromoalkandium or alpha-bromoalkane acids preparation - Google Patents
Method of alpha-bromoalkandium or alpha-bromoalkane acids preparation Download PDFInfo
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- CS242218B1 CS242218B1 CS848812A CS881284A CS242218B1 CS 242218 B1 CS242218 B1 CS 242218B1 CS 848812 A CS848812 A CS 848812A CS 881284 A CS881284 A CS 881284A CS 242218 B1 CS242218 B1 CS 242218B1
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- Prior art keywords
- bromine
- alpha
- acids
- bromoalkane
- reaction
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- 239000002253 acid Substances 0.000 title claims abstract description 20
- 150000007513 acids Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 26
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 26
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 phosphorus halides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Vynález sa týká sposobu přípravy a-brómalkánových alebo α-brómalkándiových kyselin reakciou alkánových alebo alkándiových kyselin s brómom, za přítomnosti oxidačného činidla, ktorým je chlór alebo sulfurylchlorid, pri mol. pomere brómu a oxidačnéhoi činidla 1: 0,9 až 1.The invention relates to a process for the preparation of α-bromoalkane or α-bromoalkanedioic acids by the reaction of alkane or alkanedi with bromine, in the presence of oxidizing chlorine or sulfuryl chloride reagents at mol. bromine / oxidation ratio reagent 1: 0.9 to 1.
Description
(54) Sposob přípravy «-brómalkánovýcli alebo κ-brómalkándiových kyselin(54) Process for preparing N-bromoalkanoic acids or κ-Bromoalkanedioic acids
22
Vynález sa týká sposobu přípravy a-brómalkánových alebo α-brómalkándiových kyselin reakciou alkánových alebo alkándiových kyselin s brómom, za přítomnosti oxidačného činidla, ktorým je chlór alebo sulfurylchlorid, pri mol. pomere brómu a oxidačnéhoi činidla 1: 0,9 až 1.The invention relates to a process for the preparation of α-bromoalkanoic or α-bromoalkanedioic acids by reacting alkanoic or alkanedioic acids with bromine, in the presence of an oxidizing agent such as chlorine or sulfuryl chloride, at mol. ratio of bromine and oxidizing agent of 1: 0.9 to 1.
4 2.21 84 2.21 8
Vynález sa týká sposobu přípravy .«-brómalkánových alebo α-brómalkándiových kyselin reakciou aikánavých alebo alkándiových kyselin s brómom za přítomnosti oxidačnélio činidla ako je chlór alebo sulfurylchlorid. Uvedené zlúčeniny je možné použit ako medziprodnkty pri príprave herbicídov a regulátorov rastu.The present invention relates to a process for the preparation of N-bromoalkanoic or α-bromoalkanedioic acids by reacting acanoic or alkanedioic acids with bromine in the presence of an oxidizing agent such as chlorine or sulfuryl chloride. The compounds can be used as intermediates in the preparation of herbicides and growth regulators.
V literatúre je popísaná příprava a-brómalkánových kyselin postupom podlá HellaVolharda-Zelinského, ktorý spočívá v reakcii alkánových kyselin s brómom za přítomnosti halogenidov fosforu [Volhard J.: Ann. 24.2, 141 (1887), Ward C. F. J.: Chem. Soc. 121, 1161 (1922), Marvel C. S.: Org. Syntheses 20, 106 (1940), Marvel C. S.: Org. Syntheses 21, 74 (1941), Orton J. Κ. P.: J Chem. Soc. 123, 3081 (1923),Gal H.: Ann. 129 53 (1864)).The literature describes the preparation of α-bromoalkanoic acids according to the procedure of HellaVolhard-Zelinsky, which involves reacting alkanoic acids with bromine in the presence of phosphorus halides [Volhard J .: Ann. 24.2, 141 (1887), Ward C.F.J .: Chem. Soc. 121, 1161 (1922); Marvel, C. S. Org. Syntheses 20, 106 (1940), Marvel, C. S. Org. Syntheses 21, 74 (1941); J. Chem. Soc. 123, 3081 (1923), Gal H., Ann. 129 53 (1864)).
Ako katalyzátor bromácie kyseliny octové) bola použitá síra [Genvresse P.: Bull. Soc. Chim. France (3) 7, 364 (1892)] alebo acetanhydrid a pyridin (Natelson S.: Org. Syntheses, Col. vol. III, 381).Sulfur [Genvresse P .: Bull. Soc. Chim. France (3) 7, 364 (1892)] or acetic anhydride and pyridine (Natelson S .: Org. Syntheses, Col. vol. III, 381).
Nižšie alkándiové kyseliny sa brómujú v a polohe l'ahko už pri nízkej teplote samotným brómom bez přítomnosti katalyzátorov [Willstatter R.: Ber. 35, 1375 (1902), Palmer C. S.: Org. Syntheses Col. vol. I., 240 (1932)].Lower alkanedioic acids are easily brominated at a low temperature already at low temperature by bromine alone in the absence of catalysts [Willstatter R .: Ber. 35, 1375 (1902); Palmer, C. S. Org. Syntheses Col. vol. I., 240 (1932)].
Nevýhodou doteraz známých spósobov přípravy α-brómalkánových alebo a-brómalkándiovýeh kyselin reakciou alkánových alebo alkándiových kyselin s brómom bola nízká výťažnosť reakcie, pretože z polovice brómu sa vytvára bromvodík.A disadvantage of the known processes for the preparation of α-bromoalkanoic or α-bromoalkanedioic acids by reacting alkanoic or alkanedioic acids with bromine was the low yield of the reaction, since half of the bromine is hydrogen bromide.
Teraz sa zistilo, že uvedené nedostatky odstraňuje spósob přípravy a-brómalkánových alebo α-brómalkándiových kyselin reakciou alkánových alebo alkándiových kyselin s brómom podlá vynálezu.It has now been found that the above disadvantages are overcome by the process for the preparation of α-bromoalkanoic or α-bromoalkanedioic acids by reacting alkanoic or alkanedioic acids with bromine according to the invention.
Podstata vynálezu spočívá v tom, že reakcia prebieha za přítomnosti oxidačného činidla, ktorým je chlór alebo sulfurylchlorid vo vzájomnom molárnom pomere brómu a oxidačného činidla 1 : 0,9 až 1.The invention is based on the fact that the reaction is carried out in the presence of an oxidizing agent which is chlorine or sulfuryl chloride in a molar ratio of bromine and oxidizing agent of 1: 0.9 to 1 relative to each other.
Z reakcie sa uvolňuje ako odplyn chlorovodík, resp. zmes chlorovodíka a kysličníka siřičitého. Plynovou chromatografiou sa zistilo, že chlórsubstituované deriváty kyselin reakciou nevznikajú.Hydrogen chloride or hydrogen chloride is released from the reaction. mixture of hydrogen chloride and sulfur dioxide. Gas chromatography revealed that chlorosubstituted acid derivatives were not formed by the reaction.
Výhodou uvedeného spósobu přípravy je skutočnosť, že za přítomnosti oxidačného činidla sa prevedie pri reakcii vznikajúci bromovodík znovu na bróm, ktorý opáť reaguje s alkánovou, resp. alkándiovou kyselinou. Oproti doteraz známým metodám je možné do reakcie použit polovičně množstvo brómu.The advantage of this process is that, in the presence of an oxidizing agent, the hydrogen bromide formed in the reaction is converted again into bromine, which in turn reacts with the alkane and / or alkane. alkanedioic acid. Compared to the known methods, half the amount of bromine can be used in the reaction.
Nasledujúce příklady osvetlujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the scope of the invention.
Příklad 1Example 1
Zmes 400 ml kyseliny octovej, 80 ml acetanhydridu, 0,6 ml pyridinu a 1 ml brómu sa vyhriala na 100 PC. Po odfarbení brómu sa pod hladinu reakčnej zmesi nadávkovala ekvimdolárna zmes 393,4 g brómu a 332 g sulfurylchloridu takou rýchlosťou, aby privádzaný bróm stačil zreagovať. Aby sa do reakčného prostredia vrátila časť bromovodíka strhnutého unikajúcimi plynmi (chlorovodíkom a kysličníkom siřičitým) súčasne sa do reakčnej zmesi prikvapávala zmes 260 ml kyseliny octovej a 50 mi acetanhydridu. Po ukončení dávkovania reakčných komponentov (3 hj se reakčná zmes ochladila a po přidání 30 ml vody sa, podrobila vákuovej destilácii.A mixture of 400 ml of acetic acid, 80 ml of acetic anhydride, 0.6 ml of pyridine and 1 ml bromine was heated to 100 C. After destaining L of bromine is below the surface of the reaction mixture was charged with ekvimdolárna 393.4 g of bromine and 332 g of sulfuryl chloride at a rate to the bromine fed was enough to react. A mixture of 260 ml of acetic acid and 50 ml of acetic anhydride was added dropwise to the reaction medium to return a portion of the hydrogen bromide entrained in the escaping gases (hydrogen chloride and sulfur dioxide). After the reaction components were dosed (3 h), the reaction mixture was cooled and, after addition of 30 ml of water, subjected to vacuum distillation.
Destiláciou sa získalo 192,2 g kyseliny brómoctovej v 78,8%-nom výťažku s 1.1. 118 stupňov Celzia/4,4 kPa.Distillation gave 192.2 g of bromoacetic acid in 78.8% yield with m.p. 118 degrees Celsius / 4.4 kPa.
Příklad 2Example 2
Podlá postupu uvedeného v příklade 1 sa kyselina octová brómovala s tým rozdielom, že namiesto dávkovania ekvimolárnej zmesi brómu a sulfurylchlpridu sa dávkovali pod hladinu reakčenj zmesi ekvimolárne množstvá brómu a chlóru. Reakčná zmes sa intenzívně miešala, pričom sa teplota udržiavala na 95 °C. Po ukončení dávkovania sa do reakčnej zmesi přidalo malé množstvo vody.According to the procedure of Example 1, acetic acid was brominated except that equimolar amounts of bromine and chlorine were dosed below the level of the reaction mixture instead of dosing the equimolar mixture of bromine and sulfuryl chloride. The reaction mixture was stirred vigorously while maintaining the temperature at 95 ° C. After the addition was completed, a small amount of water was added to the reaction mixture.
Destiláciou sa izolovala kyselina brómoctová v 61,1 % výťažku (počítané na použitý bróm).Bromoacetic acid was isolated by distillation in 61.1% yield (calculated on the bromine used).
P r í k 1 a d 3EXAMPLE 1 a d 3
Postupom opísaným v příklade 1 sa připravila kyselina a-brómpropiónová reakciou kyseliny propiónovej s brómom a sulfurylchloridom.As described in Example 1, α-bromopropionic acid was prepared by reacting propionic acid with bromine and sulfuryl chloride.
K 150 g kyseliny propiónovej vyhriatej na 120 °C sa přidalo malé množstvo brómu až do jeho odfarbenia., Po ochladení na, 100 PC sa pod hladinu reakčnej zmesi zavácLzala zmes 124,2 g brómu a 104,9 g sulfurylchloridu. Z reakčného prostredia odcházajúca zmes plynov obsahujúca malé množstvo brómu a bromovodíka sa protiprúdne skrápala 130 g kyseliny propiónovej. Po ukončení dávkovania sa reakčná zmes vyhrievala ešte 20 minút a podrobila sa rektifikácii. Po oddestilovaní přebytku kyseliny propiónovej pri 118 až 120 °C/5,7 kPa sa destilovala kyselina a-brómpropiónová.To 150 g of propionic acid preheated to 120 ° C, a small amount of bromine until it becomes colorless. After cooling to 100 C, right under the surface of the reaction mixture was zavácLzala 124.2 g of bromine and 104.9 g of sulfuryl chloride. 130 g of propionic acid were countercurrently sprayed in countercurrent with the gas mixture leaving the reaction medium containing a small amount of bromine and hydrogen bromide. Upon completion of dosing, the reaction mixture was heated for a further 20 minutes and subjected to rectification. After the excess propionic acid was distilled off at 118-120 ° C / 50 mbar, α-bromopropionic acid was distilled.
Destiláciou sa získalo 168 g kyseliny a-brómpropiónovej v 70,6 %-nom výťažku o čistotě 99,0 %.By distillation, 168 g of .alpha.-bromopropionic acid were obtained in a 70.6% yield with a purity of 99.0%.
Příklad 4Example 4
Zmes 35,1 g kyseliny malonovej a 100 ml dietylamínu sa ochladila na 5 °C. Pri tejto teplote sa za chladenia dávkovala zmes 27 g brómu a 23 g sulfurylchloridu.A mixture of 35.1 g of malonic acid and 100 ml of diethylamine was cooled to 5 ° C. At this temperature, a mixture of 27 g of bromine and 23 g of sulfuryl chloride was metered in with cooling.
Po zahuštění a vofnej kryštalizácii sa získalo 52,2 g kyseliny monobrómmalonovej s 1.1. 112 °C.After concentration and free crystallization, 52.2 g of monobromonalonic acid with 1.1. 112 [deg.] C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS848812A CS242218B1 (en) | 1984-11-19 | 1984-11-19 | Method of alpha-bromoalkandium or alpha-bromoalkane acids preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS848812A CS242218B1 (en) | 1984-11-19 | 1984-11-19 | Method of alpha-bromoalkandium or alpha-bromoalkane acids preparation |
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| Publication Number | Publication Date |
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| CS881284A1 CS881284A1 (en) | 1985-08-15 |
| CS242218B1 true CS242218B1 (en) | 1986-04-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS848812A CS242218B1 (en) | 1984-11-19 | 1984-11-19 | Method of alpha-bromoalkandium or alpha-bromoalkane acids preparation |
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- 1984-11-19 CS CS848812A patent/CS242218B1/en unknown
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| Publication number | Publication date |
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| CS881284A1 (en) | 1985-08-15 |
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