An inert organic solvent may be used. MDL number MFCD00011323. Hydrogen chloride gas was introduced to the reactor from the bottom and the water produced was recovered from the top section as a hydrochloric acid solution. x��\�o7��W��އ�4��/ ��c/{Al`s0�A��-")��C��je4cΔ%+���f汊���MV��O����T���e�3~��uJ��L�M!�)�I��`���L)V��挶)M.����yJF�q�E�a�����d�F�0��G\4t��i�2��/:�h�5��ѽ��o���hUi���L���Q�OC��_d�nF�i���P�ٹ9N��e*��Y���Y��h�, Jian-Lian Dong, Li-Si-Han Yu, and Jian-Wu Xie. Hg. endstream ͐,.�. endobj endstream endobj 22 0 obj �r� ��w3T�PI�2T0 BCcC#=s#C#��\. Hg was obtained. endstream PubChem Substance ID 329751739. to react HCl gas with pentaerythritol.

Anhydrous HBr (510 parts) was added continuously over a period of 12 hours at the maximum rate so as to maintain the temperature of 110° to 120°C. The HBr is fed continuously to the reactor throughout the reaction. 39 0 obj The HBr fed was a 40% excess over the amount required for di-brom formation.

Product Specifications. Preparation of dioxolanes and dioxanes was achieved using the novel solution. and a pressure of 10 to 18 p.s.i.g. Hydrogen bromide, 31 to 34 wt% (HBr), BrH, CAS Number-10035-10-6, 64-19-7, acide bromhydrique, acido bromidrico, anhydrous hydrobromic acid, bromowodor, bromowodor polish, bromwasserstoff, broomwaterstof, hydrobromic acid, hydrobromide, hydrogen bromide, 2.5L, Vapor Pressure: 300mmHg at 20 deg.C. 45 0 obj <>stream MDL number MFCD00011323. �r� Issue10.1021/acsomega.8b00159 Process for preparation of [1-(mercaptomethyl)cyclopropyl]acetic acid and related derivatives, Application filed by Formosa Laboratories Inc. This corresponds to a 50 to 100 mole percent of carboxylic radical per mole equivalent of pentaerythriol. endstream The temperature was raised to 105°C. <>>>/BBox[0 0 625.44 818.36]/Length 46>>stream ͐,.�. and found to contain 0.2% dibromoneopentyl moiety and 99.8% tribromoneopentyl moiety by weight. 5 Howick Place | London | SW1P 1WG. Example 6 -- Saponification of Tribromoneopentyl Acetate. x�S�*�*T0T0 B�����i�����U��� n)S�T ��� At the end of 12 hours, the APHA color had increased to greater than 3,000. and anhydrous HBr passed in at a rate such that the gas passed through the system and into the water filled acid trap at about 6.8 g./min. Organic recovery was about 90%. endobj (b) heating the mixture from the step (a) to about 120° C. to 200° C. x�s endstream

In addition to the product, 70 g. of a non-distillable black tar was obtained. x�S�*�*T0T0 B�����id�����]�"� �' ] This application is a

The product was a soft tan colored material weighing 738 g. which did not change color upon addition of epichlorohydrin. x�s of aqueous acid had been collected in the Dean-Stark tube. x�s �%

endobj endstream 764,664. Thus, British Pat. Although the use of a catalytic amount of a carboxylic acid or its anhydride to catalyze the reaction along with the continual feed of the HBr and the concomitant nonremoval of water during the reaction is the focal point of the present invention, the presence of an inert solvent is also important. endstream

Privacy Policy New method for synthesising ivabradine and its added salts with a pharmaceutically acceptable acid. 46 (1913), pp. The reaction mixture turned brown within 30 minutes was a dark brown cloudy liquid within 1.5 hours. A Simple and Versatile Method for the Formation of Acetals/Ketals Using Trace Conventional Acids Jian-Lian Dong, Li-Si-Han Yu, and Jian-Wu Xie* Department of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, P. R. China 99-100.

136, pp. of methanol. For example, water or perchloroethylene as shown in the examples above can be replaced by other solvents such as saturated hydrocarbon solvents like benzene, toluene, xylene, cyclohexane or petroleum ether or chlorinated hydrocarbon solvents like methylene chloride, trichloroethylene, chlorobenzene or hexachlorocyclopentadiene. The ratio of reactants employed in the present invention is essentially a function of the desired product. This study revealed that the brominating ability of this HBr/1,4-dioxane solution is equal or superior to that of hydrobromic acid or HBr in acetic acid. 47 0 obj �r� x��A� D��b���1M��D/ ������i���lfV��ܭ2����p�׀˵�C��Ë��UnƬ�[�E��W8y��D� �\���9 rB�_ԌH�+/�R���;'���J�1����&o/Z��U�1� ͐,.�.

This process has the disadvantage that it must be reacted at elevated temperatures and pressures.

The water formed as a result of the reaction remains in the reaction mixture until substantial completion of the reaction.

͐,.�. France, 1961, p. 1803, discloses a process whereby pentaerythritol and HBr are reacted using acetic acid in large amounts as a solvent. 48 0 obj analysis of a nonacetylacted sample showed that 4.2 mole percent of the product was an acetate moiety. Beilstein/REAXYS Number 3587158 . 5, Issue 3, Feb. 2, 1995, pp. endobj endobj Using a 100-gallon glass lined reactor equipped with an agitator, a 4 inch by 10 foot glass column (no packing), a 13 foot square condenser, a 10-gallon glass lined receiver and a 2-stage jet for vacuum, 390 pounds of perchloroethylene, 10 pounds of acetic acid (0.167 pound moles), and 450 pounds of pentaerythritol (3.31 pound moles) were charged to the reactor. 9 0 obj Reactions carried out in glacial acetic acid form large amounts of undesirable acetate by-product; moreover, in the prior art processes large amounts of tar are formed, and where such formation is obviated, it is obtained at the expense of having to use extremely high pressures. Saponification is used in all cases to transform the monoacetate formed into free trichlorohydrin. NOVEL PROCESS FOR THE SYNTHESIS OF IVABRADINE AND ITS SALTS OF ADDITION TO A PHARMACEUTICALLY ACCEPTABLE ACID, Lapse for failure to pay maintenance fees, Information on status: patent discontinuation, Expired due to failure to pay maintenance fee, (a) reacting a compound selected from the group consisting of [1-(mercaptomethyl) cyclopropyl]acetic acid and methyl [1-(mercaptomethyl)cyclopropyl]acetate with an amino alcohol in the presence of a catalyst in an organic solvent capable of azotropic removal of water and/or methanol to form a mixture; and. endobj Likewise, Japanese Pat.

Also in the same manner as shown for acetic acid, anhydrides, such as acetic anhydride, dichloroacetic anhydride, propionic anhydride and heptanoic anhydride, are used as catalysts in the reaction to obtain similar results. - No smoking. ͐,.�. x�S�*�*T0T0 B�����i�����U�"� � x�s 0.63 ppm (CH2, m), 1.24 ppm (2CH3, s), 1.44 ppm (SH, t), 2.39 ppm (CH2, s), 2.52˜2.56 ppm (CH2, d), 3.89 ppm (CH2, s), Owner name:

͐,.�.

This amount of HBr was in 27% excess of the stoichiometric amount needed to produce dibromoneopentyl glycol.

Of greatest interest because of their effectiveness and low cost are perchloroethylene and water. Optionally, the products of the invention may contain some chlorine provided that the starting pentaerythritol is a chlorinated derivative. 8 0 obj HBr is generally added to the reaction in anhydrous form, but the aqueous acid may be used. 34 0 obj VoR Analysis of soaps with hydrogen bromide in glacial acetic acid. �% The preparation of brominated pentaerythritols has been carried out by reacting fuming hydrobromic acid with pentaerythritol at temperatures of 120° to 160°C. ͐,.�. It obviates the use of high pressures in the reaction; however, because they remove the water that is formed during the reaction continuously throughout the reaction by passing large excesses of HCl to sweep it out, the Japanese obtain large amounts of tar formation at low levels of acetic anhydride. x�s The solution of HBr in 1,4-dioxane is robust, exhibiting no decomposition of the solvent, and retaining 97% of its original concentration, when kept at −25 °C for 30 days. 6 0 obj

͐,.�. No crystallization occurred.

Items. Normally, the reaction is run at atmospheric or superatmospheric pressure.

endstream Of course, monobromopentaerythritol and dibromoneopentyl glycol are brominated as intermediates in the reaction. 35 0 obj ͐,.�. endstream

in the presence of at least 10 mole percent of an aliphatic monocarboxylic acid or ester of same per each mole of pentaerythritol. ��w3T�PI�2T0 BCcC#=s#C#��\. Bincer et al., Ber. The HBr feed was stopped and the reaction cooled to room temperature under a nitrogen blanket overnight. <>stream Beilstein/REAXYS Number 3587158 . To show the efficiency of the carboxylic acids as catalysts, Examples A and B were separately prepared in two-liter flasks equipped with a stirrer and a condenser followed by a water scrubber to adsorb any unreacted HBr that passed through the system as follows: Example A charge was 544 g. of pentaerythritol (4 moles), 350 ml. <>stream %���� 549/511, 560/264, Click for automatic bibliography The reaction mixture was then distilled to remove the HBr as an azeotrope with the perchloroethylene and the water that was formed as a result of the reaction until the final conditions of 110° and 25 mm. of epichlorohydrin were added to neutralize the remaining acid and the product allowed to stir for 20 minutes at 100°C.