SU789474A1

SU789474A1 - Method of preparing 1,1,2,3-tetrabromopropane

Info

Publication number: SU789474A1
Application number: SU782626749A
Authority: SU
Inventors: Тамара Трофимовна Васильева; Галина Александровна Трапезникова; Борис Викторович Нелюбин; Феликс Казимирович Величко; Александр Борисович Терентьев; Рахиль Хацкелевна Фрейдлина
Original assignee: Ордена Ленина Институт Элементоорганических Соединений Ан Ссср; Всесоюзный Научно-Исследовательский Институт Йодобромной Промышленности
Priority date: 1978-06-12
Filing date: 1978-06-12
Publication date: 1980-12-23

Description

Изобретение относится к способу ; получения 1,1^2,3-тетрабромпропана, который может найти применение в промышленности основного органического синтеза.The invention relates to a method; obtaining 1,1 ^ 2,3-tetrabromopropane, which may find application in the industry of basic organic synthesis.

Известен способ получения 1,1,2,3тетрабромпропана бромированием 1,2,3и 1,1,2-трибромпропанов над Aibrjl] .A known method for producing 1,1,2,3tetrabromopropane by bromination of 1,2,3 and 1,1,2-tribromopropanes over Aibrjl].

Реакция идет сложно, с осмолением. Продукт реакции трудно отделяется от агрессивного выход тетрабромпропана не указан, строение полученного продукта не доказано.The reaction is complicated, with resinization. The reaction product is difficult to separate from the aggressive yield of tetrabromopropane is not indicated, the structure of the obtained product is not proven.

Наиболее близким к описываемому способу по технической сущности и достигаемому результату является сп соб получения 1,1,2,3-тетрабромпропа на в смеси 1,3-дибромпропеном действием брома иРСЙиа акролеин при 1820°С (2J. *The closest to the described method in terms of technical nature and the achieved result is a method for producing 1,1,2,3-tetrabromoprop in a mixture of 1,3-dibromopropene by the action of bromine IRSi acrolein at 1820 ° C (2J. *

Недостатки известного способа заключаются в том, что главным продуктом реакций является дибромпропен, а выход 1,1,2,3-тетрабромпропана не превышает 25% от теоретического,акролеин не является легко доступным сырьем и его хранение сопряжено с известными' трудностями вследствие его способности к поликонденсации,бромирование ведется с использованием аг- 30 peccHBHoro'PcC'jj что требует устранения влаги воздуха и сильно усложняет очистку целевого продукта вслед· ствие необходимости удаления галоге5 новодородных и фосфорных кислот.The disadvantages of this method are that the main reaction product is dibromopropene, and the yield of 1,1,2,3-tetrabromopropane does not exceed 25% of theoretical, acrolein is not an easily accessible raw material and its storage is associated with known difficulties due to its ability to polycondensation, bromination is carried out using ag-30 peccHBHoro'PcC'jj which requires the elimination of air moisture and greatly complicates the purification of the target product due to the need to remove halogen5 of hydrogen and phosphoric acids.

Цель изобретения - расщирение сырьевой базы для,получения 1,1,2,3тетрабромпропана, увеличение выхода и упрощение выделения целевого про1θ (Дукта.The purpose of the invention is the expansion of the raw material base for the production of 1,1,2,3tetrabromopropane, increasing the yield and simplifying the allocation of the target pro1θ (Duct.

Поставленная цель достигается описываемым способом получения 1,1,2,3тетрабромпропана, состоящим в том, 15 что бромоформ подвергают взаимодействию с этиленом при 80-120°С в присутствии смеси пентакарбонила железа и алифатического амида, взятой ,при мольном соотношении компонентов 20 1:3-3,2, в количестве 2-10 мол.% в расчете на реакционную массу, затем дегидробромируют полученный при этом 1,1,3-трибромпропан при 0-20°С гидроокисью щелочного металла в среде 25 метилцеллозольва с последующей обработкой бромом образовавшегося 3,3цибромпропена при 2О-4О°С при облучении светом. |The goal is achieved by the described method for producing 1,1,2,3tetrabromopropane, consisting in 15 that the bromoform is reacted with ethylene at 80-120 ° C in the presence of a mixture of iron pentacarbonyl and aliphatic amide, taken at a molar ratio of components 20 of 1: 3 -3.2, in an amount of 2-10 mol.% Calculated on the reaction mass, then the resulting 1,1,3-tribromopropane at 0-20 ° С is dehydrated with alkali metal hydroxide in methylcellosolve 25 medium followed by bromine treatment with 3 , 3cibromopropene at 2O-4O ° C at exposure to light. |

Способ осуществляется в три этапа.The method is carried out in three stages.

789474' ра кипения 87°С/1 мм, 1,6200,789474 'boiling point 87 ° C / 1 mm, 1.6200,

2,7238. /2.7238. /

Т . 1,1,З-Трибромпропан. В качающийся автоклав из нержавеющей стали емкостью 0,5 л, предварительно продутый этиленом, загружают смесь 433,5 г бромоформа, 6,7 г пентакарбонила железа и 7,5 диметилформамида, затем вводят этилен до давления 60 атм при 5 20°С и нагревают автоклав 4 ч при 100°С. Из полученного теломеризата отгоняют 180 г непрореагировавшего бромоформа, перегонкой остатка получают 206 г аддукта - 1,1,3-трибром- 10T 1.1, 3-Tribromopropane. A mixture of 433.5 g of bromoform, 6.7 g of iron pentacarbonyl and 7.5 dimethylformamide is loaded into a 0.5 L stainless steel oscillating autoclave pre-purged with ethylene, then ethylene is introduced to a pressure of 60 atm at 5-20 ° C and heated autoclave for 4 hours at 100 ° C. 180 g of unreacted bromoform are distilled off from the obtained telomerizate, 206 g of the adduct, 1,1,3-tribromo-10, are obtained by distillation of the residue.

Найдено 47,11%.Found 47.11%.

46,43%46.43%

Элементарный анализ.Elementary analysis.

Найдено, %: С 10,06; 38,52.Found,%: C 10.06; 38.52.

вычисленоcalculated

Н 1,09;H 1.09;

пропана.propane.

Выход 75% на прореагировавший бромоформ, температура кипения 90°С/13мм, п*° 1,5720, d₃2,3820.Yield 75% on the reacted bromoform, boiling point 90 ° C / 13 mm, n * ° 1.5720, d ₃ 2.3820.

Найдено MRa 38,79%, вычислено - -· 39/35%.Found MRa 38.79%, calculated - - · 39/35%.

£,Дибромпропен. К 56,2 г 1,1,3дибромпропана прибавляют постепенно при перемешивании и охлаждении ледяной водой до 0-2®С 13 г КОН в 50 мл метилцеллозольва, потом перемешивают 3 ч, постепенно поднимая температуру реакционной среды до 20°С, разлагают 200 мп воды, органический слой отделяют, промывают водой и сушат СаС8₂, перегонкой выделяют 20 г (50% от теоретического дибромпропена, температура^- кипения 53-57° С/14 мм.£, Dibrompropene. To 56.2 g of 1,1,3-dibromopropane, gradually add with stirring and cooling with ice water to 0-2 ° C 13 g of KOH in 50 ml of methyl cellosolve, then stir for 3 hours, gradually raising the temperature of the reaction medium to 20 ° C, decompose 200 mp water, the organic layer was separated, washed with water and dried SaS8 _2, was isolated by distillation 20 g (50% of theory dibromopropyl temperature ^- boiling point 53-57 ° C / 14 mm.

Н>. 1,1,2 , З-Тетрабромпропан. К раст-. вору 20 г дибромпропена в 50 мл ледяной CHjCOOH прибавляют по каплям при перемешивании при 2 0^е* С . 15 г брома в 15 мл ледяной СН₃С00Н, заканчивая реакцию при 4 0°С и освещении лампой накаливания мощностью 100 ватт. Процесс занимает. 2-2,5 ч. Реакционную смесь разбавляют 200 мл воды, экстрагируют СНС^, экстракт промывают 5%-ным раствором соды, затем водой, и,наконец, сушат над CaCtfg. После отгонки хлороформа остаток перегоняют в вакууме и выделяют 32 г (89% от теоретического) 1,1,2,3-тетрабромпропана, температуВычислено,%: С 10,02; Н 1,12,'В” 88,86 .N>. 1,1,2, Z-Tetrabrompropane. To the rast. to a thief, 20 g of dibromopropene in 50 ml of ice-cold CHjCOOH are added dropwise with stirring at 2 0 ^e * C. 15 g of bromine in 15 ml of ice-cold CH ₃ С00Н, ending the reaction at 4 ° С and lighting with a 100-watt incandescent lamp. The process takes. 2-2.5 hours. The reaction mixture was diluted with 200 ml of water, extracted with CHC ^, the extract was washed with 5% soda solution, then with water, and finally dried over CaCtfg. After distillation of chloroform, the residue was distilled in vacuo and 32 g (89% of theory) of 1,1,2,3-tetrabromopropane were isolated, temperature Calculated,%: С 10.02; H, 1.12; 'B', 88.86.

Строение подтверждено спектром ПИР.The structure is confirmed by the PIR spectrum.

температура кипения 90®С/13мм₍0, 2,3820.boiling point 90 ° C / 13mm ₍ 0, 2.3820.

Claims

The invention relates to a method for producing 1, IT, 3-tetrabromopropane, which can be used in the industry of basic organic synthesis. A known method of producing 1,1,2,3 tetrabromopropane by booking 1,2,3 and 1,1,2-tribromopropanes over. The reaction is difficult, with resin. The reaction product is difficult to separate from the aggressive l tbtiy yield of tetrabrompropane not indicated, the structure of the obtained product not proven. : The closest to the described method to the technical essence and the achieved result is the method of obtaining 1,2,2,3-tetrabromprop & in a mixture of 1,3-dibromopropene by the action of bromine acrolein at 18 ° C G23. The disadvantages of this method are that the main reaction product is dibromopropene and the yield of 1,1,2,3-tetrabrompropane does not exceed 25% of the theoretical one, acrolein is not an easily accessible raw material and its storage is well known. Due to its ability to polycondensate, Chroming is carried out using aggressive RO. J requires the removal of air moisture and greatly complicates the purification of the target product due to the need to remove hydrogen halide phosphoric acids. The gut of the invention is an expansion of: a base for obtaining 1,1,2,3 tetrabromopropane, increasing the yield and simplifying the allocation of the target product. This goal is achieved by the described method of preparing 1,1,2,3 tetrabromopropane, in that bromoform is reacted with ethylene at 80-120 ° C in the presence of a mixture of iron pentacarbonyl and aliphatic amide, taken at a mole ratio of 1: 3- 3.2, in the amount of 2-10 mol.% In the calculation of the reaction mass, then dehydrobromide the resulting 1,1,3-tribromopropane at 0-20 ° C with an alkali metal hydroxide in methylcellosolve followed by treatment with bromine of the resulting 3.3.3 brompropene at 20 -4C ° C at about light emission. (The method is carried out in the TpiH stage. T. 1,1,3-Tri-6-propane. Pumped from a 0.5 l stainless steel autoclave, pre-purged with ethylene / load 433.5 bromoform, 6.7 g iron pentacarbonyl and 7.5 dimethylformamide, then ethylene is introduced to a pressure of 60 atm and the autoclave is heated for 4 hours at 180 g of unreacted bromoform is distilled off from the resulting telomerizate, and by distillation of the residue, 1,1,3-tribrompropane is obtained. 75% yield on reacted bromoform, boiling point EO C / HEM, 5720, df2.3820. Found MRa 38.79%, calculated 39 ,. , Dibromopropene. To 56.2 g of 1,1,3 dibromopropane is added gradually with stirring and cooling with ice WATER to 13 g of KOH in 50 ml of methyl cellosolve, then stirred for 3 hours, gradually raising the temperature of the reaction medium to 20 ° C, decompose 200 ml of water, organic the layer is separated, washed with water and dried with CaCl 2, 20 g (50% of theoretical dibromopropene, temperature; boiling 53-57 C / 14 mm., W, 1,1,2,3-Tetrabrompropane) are distilled off by distillation. g of dibromopropene in 50 ml of ice is added dropwise with stirring at 15 g in 15 ml of ice CH, COOH, ending the reaction at and an incandescent lamp with a power of 100 watts. The process is consumed for 2-2.5 hours. The reaction mixture is diluted with 200 ml of water, extracted with CHSS, the extract is washed with 5% soda solution, then with water, and finally dried over CaCSn- After distilling off the chloroform, the residue was distilled in vacuo and 32 g (89% of the theoretical 1,1,2,3-tetrabromopropane, 870 ° C / 1 mm, ft 1.6300, 2 L 23 V) were isolated. MK 46.48% calculated Calculated 47.11%. Elementary analysis. Found,%: C 10.06; H 1.09; 88.52. Calculated,%: C 10.02; H 1.12; B 88.86. The structure is confirmed by the PMR spectrum. Claim 1. In order to obtain 1,1,2,3-tetrabromopropane, characterized in that, in order to increase the output of the target product, bromoform is subjected to interaction with ethylene. At 80-120 seconds in the presence of a mixture of pentacarbonyl: iron and aliphatic amide, when the molar ratio of the components is 1: 3-3.2, in the amount of 2-10 mol.%. based on the reaction mass, the 1,3-tribromopropane obtained at ET i is 1,3-tribromopropane with an alkali metal hydroxide at 0-20 ° C in methyl cellosolve followed by treatment of the resulting 3,3-dibromopropene b ohm at 20-400S when irradiated with light. 2. The method according to claim 1, characterized by the fact that dimethylformamide or hexamethylphospho triamide is used as an aliphatic amide. Sources of information taken into account in the examination of l.Mounerat A. Effects of bromine and 1,1,2-tribrompropane. Bull. soc. chim.France, (3), 19, 1898, p. 807.

2. Parfenov, EA, Yurkevich, A.M. Synthesis of 5-bromo-4-pentenoic acid and some of its derivatives, ZORKH, 2: 1971, p. 2471 (prototype).