DE1445653A1 - Process for the preparation of chlorine derivatives of alpha-picoline - Google Patents

Description

Patent attorneys
DfpLtag.F.Welckniann, Dr.ing.A.Weicktnann \

Dipl. Ing. H. Wrickrcsr. *. CIpI. Γ hp. Cr.K. Fincka I Munich 27, M & ktreSf 22

THE DOW CHEMICAL COMPANY, Midland, Michigan, V.St, A. \ Process for the production of chlorine derivatives of e-pisolin

The present "invention relates to new 2-C triofelor" ethyl) -pyridine derivatives * which have a chlorato "in the 6-" third. The invention also relates to a method for the production of 2- (Trioiaon »thj-l) -pyriiiinen, which one or more · Starting chlorine substituents c »nucleus.

The well-known direct chlorination of a-Plcoline argues plexe Oeaiech ·, low "yields of £ ii" elkoaponenten and considerable tar formation · Bs see literature no indication "that a island coaponent or a" selected group of compounds can be produced in this manner in teehnisoli acceptable yields "*. Certain of the get ·? * components idännen scwar can be obtained by fractional distillation, doeh is

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the srsattjg & e Meng® irrespective of a connection or a susipfAiteii Orupps ven. lC © 5Bpea®fifc®gi g © klein »dse © dl © methods gerlaigsn. or none. t @ © h »± s @ Ii © si Mart if-only one of the chlorinated CE-Picöliis © is desired

find slisls in. der LitemfciiE ⁵ no® Asigafeass «that al®

di © © in ChlO'ratoa in., by Chlorierungsniethoden Chlor- are produced te8nn @ Ho Ss ren midt. teia Torsohla's and no information © ir® @ fää © laer Modifi-

¥ learn «. The production of the tri

" 'allow.

is-inaM® s »s-sfffliöeiij that 6-chloro-gdin XQleht wgnä I» gates ». Yields by C! Il © ri @ riKig vm e-Fi © © iiia © teF s @ ii & t§i -Ohlorierungspordultten means © chlorine bsi erihShtssä '^^ peraturen. kSnnenO BIf 6 ^ St @ lIis2ig des, .H®rns. will- part d

by chlorination © to @ s

materials oS © r -Swlsehsnprodiskfcs unter Condingnnigesi with chlorine subs & It ^ l © i »t _s eä £ e. the removal of HCi asis ds® 2 «aethyl} -p3rridine> AuegangsiBaterial..or. - Intermediate product

borrowed: or - bagftastigen · '· -. ■

BATH ORIGINAL

For ^lt Cihlor-6-2 "(ti'Ichlormethyl} * pyridines ^ft gehöre® liier ¹ · Each any or all of the following Verbindungens ö-chloro-2- (trichloromethyl) -pyrldlnf

pyridine; You-dichloro-S

chloro-2- (triohlomethyl) -pyridlnj>, * "5 * 6 ~ T" fc3? ahlor-2- (trlehlomethyl) -pyridln.

The new process enables the manufacture of a single Compound or a select group of compounds - in excellent yields, It is noteworthy * that »at now such connections with minimal tarred oil and minimal formation of undesired chlorinated pleolin by-products, which do not have a chlorine atom in the 6-position can.

Bs is believed to be strong concentrations of aqueous HCl, which is involved in the reaction at lower temperatures and in the presence of water can form, or the accumulation of Bsolecular HCl, which in decs reaction mixtures in the absence is formed by or added to water, a salt or another addition product with the 2- (tri-chloromethyl) pyridins can form. It is possible that the HCl addition product is chlorination at the 6-position not allowed. The implementation of the chlorination according to the invention des 2- (Trichlorinethyl) -pyridine under conditions,

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the removal of HCl from the 2- (trichloroethyl) pyridine reaction component enable or favor »can have the effect, at least a part of the Heaktionskoraponente in the form of the free base * conditions that the Removal or escape of HGl from the reaction gel *

BJisöh favor, child in the description below illustrated. Based on this assumption, the shape of the free base are in turn easily chlorinated in the 6-position. It has not yet been established and it has been done so far no information is given about this difference in the reactivity of the 6-position and the other positions of the nucleus with 2- (trichloromethyl) pyridines. It has also been so far not determined that the concentration of HCl in the Reaction mixture can have such a direct effect on the reactivity of the 6 ~ position in the chlorination reaction.

It has now also been found that the substitution of chlorine atoms on <3 "n nucleus of the α-pieoline in the 5", 4- and / or 5-position is generally before and not after the end of the peroloration of the methyl group in each a -Picolinraolekttl takes place. It has also been found that the introduction of chlorine into the 6-position is only possible after the methyl group of the a-picolinra molecule has been perchlorinated _c

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Although it is desirable according to the invention, the removal of To favor or promote HCX from the reaction mixture, In order to avoid an excessively bone HCl concentration during the substitution stage of chlorine in the 6-3 position of the 2- (trichloromethyl) -pyrldine reaction components, but it has been found that it is often advantageous if HCl is present during the initial chlorination stage leads to nuclear substitution by chlorine and to chlorination of the methyl group of the a-picoline starting material. This is done in the explained in more detail below. Usually it is necessary to know that the conditions during the chlorination are such that HCl from the a-Plcolin or from the 2 ~ (mono- or »(Diohlormethyl) -pyridinen, which in the reaction mixture are not removed.

Excellent results are due to the invention Process achievable when the chlorination is in the liquid phase

is carried out with or without the use of an inert solvent. The chlorine is advantageously in the form of gaseous chlorine used and passed through the reaction mixture. This also enables the removal of HCl or the reduction of the HCl concentration in the reaction mixture, which contains the 2- (trichloromethyl) pyridines to be chlorinated in the 6-position, by passing a noticeable excess of gaseous chlorine through the reaction equipment.

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The substitution ν cn chlorine in the 6 "3tellung of 2- (TrIChOrmethyl)" pyridine is favored * and wag © yields cn the g € wüi ^ 83h £ s _t i 6-StsIlung öhlormifestitui & rfeen 2- {trichloro-B6thyl) pyridines can obtained if the chlorination is carried out under pr & ktisoh anhydrous conditions *

The same or even better results can be obtained when the chlorination is carried out according to the correct method, hot 56 * rkllcr ·. elevated temperatures is carried out, ie h & t i & nper & fuuren * which are higher than the partial pressures used in the known direct chlorination of oc ~ PiooXIa.

The proper experience can be in the presence or absence Entity of a catalyzing light source carried out who> The iron advantage in visual cases is chlorination in the 6-3 position of the 2-Cfriohloraethyl) -> p3rrldin3 in the presence from radiation, such as actinisohem or ultraviolet ' tea light, diirohsuf clocks.

An important embodiment of the present invention concerns the verifenduni of α-picoline as the starting point "ri &l" this fc * rm host "! advertise liquefied, % after @ m suerst sin »Piooliö-hfärochlortd-Mass» is formed, for example, by saturation v @ a a-Pioolin with HCl prior to the chlorination. This saturation of the a-plcoline ait HOl can easily be observed

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a temperature of 20 to 70 ⁰ C can be carried out.

According to the invention, the new compound is a chlorinated one a-picoline of the formula

[6-chloro-2- (trichloroethyl) pyridine 3 available.

According to the invention, this new compound can easily be reduced or reduced by perchlorination of the side chain of the a ^ pleolina no substitution in the 3-, 4- and / or 5-position des Kerns or by using 2- (trichloromethyl) pyridine be produced as starting material in the further chlorination. This modification enables the manufacture of 6-chloro-2- (triohlonaethyl) -pyridine in high yields in practically pure form or of mixtures containing high proportions of 6-chloro-.2 "(tri-chloro-methyl) -pyridine, depending on the The special conditions used in carrying out the process, 2 ~ (trichloromethyl) ~ pyridine is used as the starting point

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Material used, good yields can be achieved by carrying out the chlorination at temperatures above 155 * C and in particular at a temperature between 135 and 180 * C. _# Is chlorinated at a temperature in the range of 135 to 18O * C the reaction can be facilitated, and further improved yields are often obtained when the chlorination is carried out under substantially anhydrous conditions.

In another preferred process for the preparation of the new 6 "chloro" S- (triehlonsethyl) -pyridine, either a-picoline or 2- (trichlone-methyl) -pyridine is used as the starting material; this process differs from the previous process in that the chlorination is carried out at an even higher temperature, above the boiling point of any aqueous KCl that may be formed or present in the reaction mixtures. This process provides excellent results chlorination of a-picoline or 2 ~ (trichloromethyl) -pyrldin at temperatures above iso ^E C. Pie introduction of chlorine in the 6 position of the ~ 2- (trichloromethyl) »pyridine in the liquid phase can indeed advantageously at a temperature in the range of 180 to 230 * C are carried out, but the use of a temperature of I90 results in up to 210 ⁰ C higher Mengenantoile of 6-chloro-2 "(tr" ichlorinethyl) -pyridine with less formation of

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unexpected onaohtea by-product.

The sweeping binding of gaseous chlorine in da-a-Floolln for the production of 6-chloro-2- (triohloraethyl) -pyrldsjri depend on many factors, such as For example, temperature, operating greetings and the like., From. Yes • In general, the use of gaseous chlorine is used • In a quantity of 1 to 2 oewloht places per 1 oewloht part a-Pioolln bsw. A with HCl saturated orPieolln for good results.

In addition, the new compound is a chlorinated compound tes a-Ploolln the Fornel

JO-

[3,4,5 # 6 * ~ Tetraohlor-2- (triohlomethyl) - pyrldine] ("Heptaohlorpicolin")

available.

This new compound can be invented by the substitution of chlorine in the 3-, 4- and 5-position of the a-Pioolinrlnga,

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preferably after saturation dee α-picoline are made with gaseous HCl at low temperatures and prior to the perchlorination the rare chain "" This method erssSglicht the preparation of mixtures that are rich in 3 »^ t 5,6-Tötrachlor-2- (triehlonnethyl) pyridine (heptaehlor pie & lin) and 3 »4,5-triochloro-2- (triochloromethyl) pyridine (ifexaohlorpicolin) and also some 3,4,5« ti'iahlor ~ 2- (dulonethyl) ° pyrldln (pentaohlorporoline ) contain. The Heptsohlorpleolin and the other components can en Gerafeehen duroh fractionated © 'distillation t "Excellent © results can dtiroh Ans" the Chlorienmg d © se ~ Pioolins feel Teasperatisraa in Bes ^ SiOH ¥ on rsielt 90 to 120 ^e G ©, "are but simi Tesapera »in the range from 95 to 105 * C preferred in general

öer HCI-KiBSiseEifemtion in that t; Änebes-ainSerQ In ciieasEä case to be favorable and can

by using sufficient chlorine in excess of what is actually required for the chlorination reaction, the excess being 11.5 to 21.5 parts by weight of chlorine used corresponding to 1 part by weight of α-picoline. The eradication of Heptaohlorpicoliii can often be increased according to the invention by carrying out the chlorination of the α-picoline in the presence of a catalyst. Examples of particularly effective catalysts include the Lewls "* SKuren" as examples

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BAO

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wise AlCl ,, FeCl, or PCI ,. In general it is not necessary to use the catalyst in an amount of more than 5 weight percent, based on the weight of the α-piooline, and amounts of 0.3 to 1 weight percent are often sufficient, us to achieve a noticeable increase in yields.

According to the invention, chlorinated α-picolines of the formulas are also new compounds

-Cl

and

[3,6-dichloro-2- (trichloro [5 ^ 6-DiOhIOr-S- (trlohlomethyl) pyridine] »ethyl) pyridiri]

obtainable.

These connections can easily be made according to the invention are by using 2- (Triohlormethy1) -pyridines as starting material for further chlorination, which in the 3- or 5-position of the Kexjis duroh chlorine are substituted «The Introduction of chlorine in the 6-position of these materials can advantageously at a temperature of 110 to 16O "C be made. The corresponding 6-chloro-2- (trichloromethyl) pyridines, the chlorine substances in any ^ b

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Any 2 or all 3 of the 2, 4 and / or 5 positions can be produced in an analogous manner by using the corresponding chlorosubstituted 2- (triehlomethyl) pyridines as Auagange "at" riallea and work as described below.

However, the exact preferred temperature range will vary depending on the starting material used. If, for example, 3-chloro-, 5-chloro-, 5,5-dichloro- or 3,4 _# 5-1ri3hlor-2- (trichloroethyl) pyridine is used as the starting material, the particular preferred temperature range for effecting the introduction of chlorine is In the 6-position 110 to 120 * C, 120 to 150 * 0, 1 ^ 5 to 145 * C etc. 150 to 16O * C. These chlorinations can also advantageously be carried out in the liquid phase with gaseous chlorine under practically anhydrous conditions. When the process is carried out in this way, gaseous "chlorine" is used, preferably in an amount of 0 * 5 to 2 hol per mole of 8- (triohlorethyl) <"2} yi * idln reaction component *"

Oils of the invention, process catfish described above Tune easily continuously with continuous feed Put the respective starting materials and the chlorine and any other additives in a reaction vessel and counterbalance

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lichee sieving of the chlorinated picolines can be done *

As already mentioned, an important way of carrying out the process according to the invention enables the production of practically pure 6-chloro-2- (trichlone-methyl) -pyridine in excellent yields directly from a-Picolln in a single continuous process or in a batch from guided proceedings. In addition, a mixture enriched in 6-chloro-2- (trichloroethyl) -pyridine, which also contains smaller amounts of 3 * 5-di-chloro-2- (trichloroethyl) "- pyridine and 2- (Triohlormethyl) -pyridin can contain «if desired can also be produced.

Accordingly, the chlorination of a-pioolin can be carried out quickly and economically with the formation of an Oemisohs which is oxidized to 6-chloro-2- (trichlonethyl) -pyrldln in one process "in which a-ploolin and gaseous chlorine are continuously and simultaneously at noticeably distant points be introduced into a reaction system, whereby a reaction in the liquid phase with the formation of the · desired! on 6-chloro-2- (trlohlonBethyl) ~ pyrldine ang »- relohertea Oenlsoha takes place. Is la following the off "druok" Pioolin "is used, it is to a ^N-picoline mean ^tt. In the "process a liquid Plcolin-hydroohlorld mass is formed first" the mass is then converted into a liquid phase

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system introduced and gaseous chlorine passed through the Plüssigphasessystesi under controlled temperature conditions to generate in the desired 6-Ciilor-2- (fcriohloreethyl) -pyridine enriched mixture. By "liquid picolines hydrochloric * pulp" is a liquid mixture or a honogenes LSsung screened one "that arises when Fioolin-hydroohlorld, which is usually a solid substance iot _p in contact Bit excess hydrogen chloride gas accommodated.

In this execution of the srfindimgegestüisaen process, chlorine gas is introduced into a suitable liquid syatess, which contains a Xiiitiatorbe @ chi # ktmg "as described in the following," is cooled in the gaseous hydrogen chloride system, which is then cooled in situ into a system led and iai Cte ^ asiBtroa lait Fioolisi is brought into contact "to form a liquid? icolin-hyä? ö®hlorid" M $ s6 $ su "the south heated liquid Syetera asurücik led, whereupon it becomes a gaseous one Chlorine reacts in the formation of the desired product enriched in 6-chloro "2>(triohlonsethyl)" pyridine.

The ⁿ Znltiatorhegchickung ^n, which in the PriKärreaktionegefKss! Mr initiation dee erfindungagösKseen Terfah ^ esis is introduced "is a liquid material reacts" with the "2tas" iMenbrlnge & Bit gaseous chlorine to form hydrogen chloride.

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BATH

While this requirement can be met with a myriad of materials, for practical reasons it is a "picoline coating" and materials are recommended preformed 2- (trichlonaethyl) pyridine or preformed liquid pioolin hydrochloride mass, the duroh treatment Pioolin Bit can produce a very high molar excess of hydrogen chloride. The Inlatorbeschlckung used in this catfish should be one of solid pioolin hydrochloride free liquid medium. In addition, the entire process should be carried out in such a way that no solid Pioolin-hydroohlorld or solid Tar can get into the reaction vessel. It was found that the presence of these pesticides intensifies decomposition, for example, makes implementation more difficult.

The hydrogen chloride formed in situ is led to a cooled secondary reaction vessel, which is a partial cooler, in which it is brought into contact with pioolin in an atmosphere of excess hydrogen chloride to form a liquid picolin hydrochloride mixture under set temporal conditions At the 1st stage, hydrogen chloride from a major source can be used, but this is not necessary since once the reaction has begun there is always an abundant internal supply of hydrogen chloride. In this stage, pioolin hydrochloride is formed at the beginning, but a liquid mass is formed in the presence of excess hydrogen chloride. The presence

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BATH

Excess hydrogen chloride ensures the smooth conversion of pioolin into liquid pioolin hydrochloride cheeses. An effective means of bringing hydrogen chloride and fioolin into contact is a rapid transfer of the resulting liquid pieoline hydrochloride mass to the primary reaction vessel can be achieved by controlling the temperatures so that a considerable proportion of the initial volume is obtained Heat of the reaction between Pioölin and hydrogen chloride removed, but so much heat is retained that the formation of a liquid mass is enabled and the mass is kept in a liquid state during the "flow path" to the primary stream. The achievement of the desired temperature control can The best way to accomplish this is to use a heating vessel of such size and / or dimensions as to provide a high level of positive temperature control throughout the reactor. Since the reaction of picoline hydrochloride formation is exothermic and chlorine gas is present, which favors the formation of Taei ¹ in over-temperature temperatures, it is important that the reaction flow has a relatively small area of cooling surfaces or walls where the outside of the cooling is located A suitable temperature range for carrying out this stage is from about 20 to about 70 ° C. It is essential that noticeably higher temperatures are allowed to lead to the formation of undesirable lifting products or

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To prevent mechanical difficulties which result from such by-product formation. Temperatures below 20 ° C should be avoided in order to eliminate mechanical difficulties which arise from the deposition of solid pioolin hydrochloride or from chemical difficulties which are seldom caused by solid Pioolin hydrochloride falling into the PrimKrreaktionsgefKss or in this can be caused. A constant temperature of about 30 ^{9 is} suitable. The introduction of significant amounts of unchanged tea pioolin into the premix reaction vessel instead of the liquid composition usually leads, as was heated, to low yields and frequently uncontrollable mixtures.

The exact rate of supply of the chlorine into the primary reaction vessel depends on the particular operating parameters, the shape of the reaction vessel, whether mechanical fishing is used or not, and the like. ^F or effective operation, it let zweckmltssig to provide a sufficient flow of chlorine gas rasohen * to maintain a rapid transfer of the Pioolin-hydroohlorid to ensure * in the desired Hasse, good movement and continuously hydrochloric lead away from the reaction vessel. Two-kilometer rates of introduction can be based on the rate of supply of the ploolin reaction coraponent into the reaction system

be expressed. As a single speed, a

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Haltnia from chlorine to pieolin from about 1: 1 to about 2 ί 1 Oewlohtsbaale viewed. A typical example of a purpose »!! ·· Average speed is around 1.8 kg to 3.2 kg (4 - 7 pounds «)

Chlorine per hour at a pioolin boiling rate of about 0.9 to 3.2 kg (2 - 7 pounds) per hour when introduced into a 24! ) Reaktlonsgeisoh contains. The residence time depends on the volume of the reaction mixture and the speed required to maintain the stationary condition; from «under" steady state "the state is eased, which is created when the addition of the reaction mixture is more noticeable. The to achieve a sfce, fci © nii «®ii Zuel-aada

The time depends on the conditions that are used in the wiMen, and can easily be determined in order to achieve a total of 17 to 35 hours above and in the following conditions.

irgeMies®. ühto? Depending on the preferred working conditions, the intended residence time is around 17 hours.

The orfolgrelohe selective production of an Oemisohe enriched in 2-chloro-6- (trlohlormethyl) -pyrldine is carried out by Careful adjustment of the temperature of the reaction mixture, i.e. the temperature of the preliminary reaction vessel, is facilitated. Relatively high temperatures should be maintained in the reaction vessel at all times. Within the usable temperature range of about I4o to 230 * C further constraints srar more selective control of the commercial

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SAD ORIGINAL,

th product composition. Thus, by carefully choosing the temperatures, the process can be carried out to produce 6-chlorot- (trichloromethyl) -pyridine practically as the only product, or to produce compositions which contain 3,5-diehlor-2- (trichloromethyl) -pyridine and 2- Contains (trichloromethyl) pyridine in noticeable but minor proportions. In general, good Auebeuten to a mixture that is close accumulates 6-chloro-2- (triohlora> ethyl) -pyridine can be obtained by ,, the reaction is carried out in the temperature range of about 16O to about 200 C ^9. Optimum temperatures for the recovery of 6-chloro-2- (tri ~ ohlormethyl) -pyridine be from about 180 to about 190 ⁰ C, measurable amounts of 3,5-Diohlor-2- (triohlanaethyl) -pyridine and 2- (Trichlormethy1) -pyridine can be achieved in the product by lowering the reaction temperature, in particular to below about 170 ° C.

The reaction can be carried out in the presence of ultraviolet light. However, it was found that on the contrary « set too many chlorination reactions no advantage is achieved thereby. When implementation in the presence of light is carried out, the light source can also serve as a WKroe source.

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The thus obtained enriched in 6-ChIOr-S- (trioMonaethyl) -pyridine The mixture is a water-white liquid and can contain small amounts of 3, S-ßlchlor-S-Ctrichloromethyl) pyridine and 2- (TrichlQrraethyl) -pyridin contain. The procedure can also can be modified to practically pure 6-chloro ~ 2- (trichloromethyl) pyridine as the only product su produce.

In the case of a modification according to the invention, a method for the continuous recovery of δ-chloro-S-trichloromethyl) pyridine as a practically pure product, the chlorination in the reaction vessel, as explained above, is preferably carried out at a reactor temperature in the range from about 190 to about 210 ° C. The mixture obtained is discharged directly from dam Reaktionsgefäsß and placed in the center of a distillation column * the at bubbles "or Gefasstemperatür in the range of I80 to 190 ° C, at a temperature at the upper end © of the column in Bsreioh of 125 bis.130 ⁰ C and at a Dmok of about 8 to 10 sma Hg abs, whereupon a smaller mezigenant of the more volatile 2- (trichlonsethyl) pyridine is preferably distilled off and retained in the passing fraction and the less volatile 6-chloro-2- (triehlorraethyl) pyridine and by-products are obtained as residue fraction. The residue fraction can be withdrawn at the temperature of the vessel or, without cooling, in the center of a second distillation colony

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be introduced «which works at about 20 to 22 mm Hg abs pressure at a temperature at the upper end of the column of about 150 ° C and at an OefSa temperature range from about 200 to 220 ⁹ C to produce practically pure 6-chloro-2- (Triohlormethyl) -pyridin überzudestlleren and recovered as a passing fraction and smaller amounts of by-products in the higher-boiling residue fraction. The resulting 6-chloro-2- (trichloromethyl) pyridine 1st a water-white liquid, which separates fled upon cooling to room temperature as white crystalline solid substance of F »60.7 to 62 ^# C without recrystallization. The 2- (trihlorethyl) pyridine, which is obtained as the fraction which passes over in the first distillation, can be returned to the reaction vessel for further chlorination to 6-chloro-2- (trichorroethyl) pyridine.

The method according to the invention can, if desired, modes be fled to significant and / or recoverable amounts of 5, S-Diohlor-S-Ctrichlorraethyl) pyridine su generate. For some operations, a product is desired that is rich in 67Chlor-2- (trichloromethyl) ~ pyrldine is and subordinate however large quantities of 3,5 dichloro 2 (trichloroethyl) " pyridin contains “For the production of solo compositions the chlorination described above can be carried out in a temperature

_{A r} made range from about 140 to about 180 C / and the resulting mixture

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by continuously withdrawing it from the reaction vessel without Distillation can be obtained. A product containing about 10 to 20 moles of # 3, S-dichloro · ^ - (trichloromethyl) pyridine can can be obtained according to this process modification. Be it noted that the product thus obtained can be continuously distilled to give the components, i.e. 6-chloro ~ 2- (trlehiormethyl) -> pyridine as passing fraction and 3,5-Diehlor- * 2 <- (triehlorraethyl) ~ pyridine by further distilling the heavy fraction.

As a further modification of the process in accordance with the invention, the chlorination can be carried out at a lower temperature than the optimum temperature given above in order to achieve good yields of 6 ~ chlorine «2" (triehlGrmethyl) «> pyridine by carrying out the chlorination in separate stages, wokai Two reaction vessels are closed one after the other and the chlorination mixture obtained from the first reaction vessel is transferred to the second reaction vessel and chlorinated in this under similar conditions to form a mixture enriched in 6-chloro-2- (trlchloromethyl) pyridine Second reaction vessel obtained or led to columns for distillation. When using two-stage chlorination, lower temperatures can be used in order to obtain high yields of the desired product without a drop in operating performance

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chlorination two-stage has been achieved even at lower temperatures without the use of a by a Destillationaetufe is applied as part of the operating method, the primarily is zurüokgeführt of 2- (trichloromethyl) pyridine existing fraction passing over into the process.

In another important embodiment of the process according to the invention, the continuous low-temperature chlorination process enables high yields of highly chlorinated fioolin compounds to be achieved, the product being enriched in 3,4,5 # 6-tetrachloro-2 - (trichloromethyl) pyridine. The Qemisoh obtained contains two further "highly ohlorierte picolines in important, but easily removable volumes and is virtually free of impurities isonseren, lower chlorinated materials and decomposition" products usually _c The product onthält 5,4,5-Triohlor-2- (triohlormethyl} -pyridine and 5,4,5-trichloro-2- (dichlonaethyl) pyridine as the other main components. This process not only allows the desired components to be prepared in good yields and in a port that is easily separable from the smaller amounts of lower chlorinated by-products » but the by-products are free of tarry decomposition products, if their use as starting materials for the manufacture of other chemical intermediates and end products

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ducts made possible. The present proceedings are the first Male a method available as a preparative method for highly chlorinated (trichloromiethyl) pyridine compound © n is useful and which also represents a useful technical production method.

3®i this embodiment of the method according to the invention α-Picoline and gaseous chlorine are continuously and at the same time in noticeably distant places in introduced a reaction system, whereby a reaction in the liquid phase to form the desired product mixture takes place. The method includes an initial formation a liquid Pioolin-Hydroohlorid-Mase®, the introduction the Hass® iix a liquid phase system and passage of gaseous chlorine through the liquid phase system in the same Way as described above.

The initial statement used in this case is preferred » does a highly chlorinated picolin composition have a? Density from 1.65 to 1.8c Such a material still has reactive hydrogen, but it avoids dl Introduction of foreign material * As soon as the procedure has started, a chlorinated Picolingeraieeh is used as initi> atorbesohiokung are available. If not an ohlorated one Picoline is available, a small amount of pioolin diluted with an inert low boiling solvent can be used, removing the solvent from the product

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the extraction of which is easily removable. "It is common It is only necessary in this case to introduce several equivalents of anhydrous HCl before adding the chlorine. Otherwise solid pioolin monohydrochloride is formed, which impairs good yields.

The hydrogen chloride formed in situ is passed to a cooled secondary reaction vessel in which it is mixed with picoline under controlled temperature conditions An atmosphere of excess hydrogen chloride is contacted to form a liquid mass of picoline hydrochloride. As before, external source hydrogen chloride can be used at this stage, but it is not necessary, since once the reaction has begun there is always an abundant internal supply of hydrogen chloride. The other considerations, such as temperature and the like, for formation and the like the portrays of liquid picoline hydrochloride hates apply in this case as well.

The exact rate at which the chlorine is fed into the primary reaction vessel depends on the particular operating size and shape of the reaction vessel, whether mechanical mixing is used or not, and the like. For effective operation these

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“AD ORIGINAL

In the process, a molar excess of about 80 to 85 % of chlorine should be present in the reaction vessel for the entire time "in order not only to ensure a smooth conversion of the picoline hydrochloride" material "but also to continuously flush hydrogen chloride out of the reaction vessel." The most appropriate Speed can be expressed in terms of awf the feed rate of the pieoline reactant into the reaction system. A ratio of chlorine to Plcolin of about 11.5 J 1 to about 21.5 t 1 on Oewlchtsbasls is regarded as such a speed. Illustrative of a suitable speed is that of about 1.8 to 2.7. 4 ~ 6 pounds of chlorine per hour at a picoline blocking rate of 0.28 x 0.35 pounds per hour when introduced into a .4 gallon reactor of contains about 17 liters (4.5 gallon) of water. The dwell time depends on the degree of reaction and the rate of feed required to maintain a steady state. The time required to reach a steady state depends on the conditions used in the system and can easily be determined. The steady state density of the reaction mixture is usually from about 1.2 to 1.4 g / onr (10 12 pounds / gallon) with an average of about 1.3 g / cm (11 pounds / gallon) »This is the density a duroh-

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Average density of the total mixture in the reactor insofar " as a liquid two-phase system of practically determined proportions with the above average densities develops when the reaction reaches a steady state. The upper liquid phase is a liquid hydrochloride composition that contains picoline hydrochloride and low-chlorinated picoline hydrochloride in excess hydrogen chloride, and the lower liquid phase contains a highly chlorinated mixture which is enriched in 3 »^ * 5» 6-tetrachlor ~ 2 ~ (triohlornethyl) -pyrldine. Assuming a as above given reactor feed composition, one Polynesial occupancy rate of about Q, 1J | kg (0.2 pounds) per hour and an average molecular weight of the product of 500, the Verwellzoite would be 50 hours.

In this process for the selective production of lines of 3f4,5,6-T * traohlor-2- (trichloromethyl) -pyridine-enriched Oenlechs, better results can be achieved by careful adjustment of the temperature of the reaction mixture, ie the temperature in the primary reaction vessel . In particular, the temperature should not be allowed to remain above 120 ⁰ C for any significant period of time "A more expedient temperature range is from about 95 to about 110 ° C. Olelohmäselg good results were obtained at 100 ⁰ C.

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28- H45653

The reaction can indeed act in the absence of a catalytic Light source can be carried out, but the use of radiation is preferred, a light with a wavelength of about 2000 to 5000 A and especially about 3000 to about 4000 A. emitting light source is suitable. When the response is in Presence of light is carried out «can be the light source also serve as a heat source "

The reaction can also be in the presence or in

t _a

a catalyst can be carried out. One of highly chlorinated pieoline compounds, in particular 3.%, 5 »6-Tetraehlonnethyl ~ 2 ~ (triehlomethyl) pyridine enriched Mixture can in good builds in the absence of a catalyst can be obtained. This is particularly true if the product obtained by this method is old due to use of known chlorination methods obtained products compared will. However, Ee has been found that by using Lewis "acid" catalysts used in the present process The yield of the desired product can be increased noticeably » In the preferred method for the preparation of a 3 * ^ # 5j6-tetrachloro-2 -> (trichlo «Bethyl) -pyridine-enriched mixtures, the use of a Lewis acid catalyst is therefore provided. Any Lewis acid © catalyst can be used will. Aluminum chlorides, phosphorus trichloride, are particularly twofold and ferric chloride. Others include stannous chloride,

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H45653

Antimony chloride, thionyl chloride, sulfuryl chloride, phosphorus pentoxide, calcium chloride, iodine, red phosphorus and the like. Salts of polyvalent metals in the lower valence level as well as free metals can be used. If the latter are used, they are evidently easily converted into the corresponding metal chloride by the hydrogen chloride formed in the reaction mixture. The catalyst is advantageously not in an amount of more than 5 wt -.% Of Picolinbeschiokung used. Preferred amounts are from 0.5 to 1 Ge * r.- £.

The resulting ^ an 5,4 »5,6-tetrachloro-2- (trichloroethyl) pyridine The enriched mixture is clear as water, has a practically constant density «contains only small amounts of low-chlorinated picolines and is practically free of hydrogen chloride. This enriched product mixture forms a lower one liquid phase in the reaction vessel, while the less chlorinated pioolin, dissolved in hydrogen chloride, the less dense upper liquid phase forms. The exact composition of the reaction vessel in the steady state Removal mixtures can easily be determined by analysis of samples by vapor phase chromatography or by density comparison with a predetermined density composition ^ Be ~ Draw will be appreciated. The average densities of the 5,4,5,6-tetrachloro-2- (trichloromethyl) -pyridine, 3t ** 5, -Trichlor-S-itrichloromethyl) -pyridine and 2,4,5-Triohlor- 2- (dichloromethyl) -pyridine as main components containing Pro-

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1U5653

ducts vary from 1.68 to 1.78 and are usually about 1.75. The product can be removed from the reactor by usual means Methods withdrawn and, if necessary, separated into its components by fractional distillation.

According to another preferred embodiment of the invention 6-chloro-2- (trichloromethyl) pyridine compounds can be used leieftt and produced in good yields by one method where it is 2- (triehlomethyl) pyridine compound the formula

-X

-CCl,

bit gins liquid® state heated and / or in liquid form is held and gaseous chlorine is passed through. the Response can be represented by the following equation

Cl,

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The selective chlorination reaction takes place smoothly, quickly and in good yields with little or no formation of by-products and no formation of undesirable tar materials if for effective contact between the appropriate 2- (Trichlora »thyiy ~ pyridium reaction component is provided in liquid state and gaseous chlorine.

When carrying out the reaction, the reaction speed can

Temperature resistance by increasing the tea temperature slightly above that! must be increased, which is necessary to keep the reaction medium in the liquid state, but in order to achieve selectivity in the chlorination it is important that severe temperature conditions are not applied.The upper temperature limit suitable for achieving the moderate selective chlorination is about 160 ° C . The lower limit is of course determined by the special starting material, but although the reaction can be carried out near room temperature, a more practical lower limit is regarded as a temperature of about 100 ° C. The preferred temperatures for conducting the reaction vary in part depending on the particular compound to be produced and are in the range from about 110 to about 160.degree. With the exception of the 2 ~ (Triohlor "tthyl) · pyridine itself, preferably (tr! Chlorinethyl) at temperatures of about 1J5 ^e C for 6-chloro-2". pyridine is chlorinated,

909808/1125

It appears that the less chlorinated reaction components have optimal reaction temperatures at the lower end of the overall preferred range, while the more highly chlorinated reaction components have preferred reaction temperatures at the upper end of the preferred range. For example, seems the chlorination of 2-chloro-2 ~ (triohlormethyl) pyridine to 5,5-Dicnlor ~ 2 "(trichloromethyl) pyridine best at temperatures between about!" To run 10 to 120 ⁰ C. Similarly, The chlorination of 5-chloro-2- (trichloro-methyl) -pyridine to give 5 -6-bichloro-2- (trichloro-methyl) -pyridine appears to proceed best at temperatures in the range from about 120 to 130 ° C. On the other hand, the chlorination appears of Jj ^ S-Triehlor-S-itrichlorsisthyl) pyridines extend to ⁰ C to "soo to 3» ö ^^-tetrachloro-S- (trichloromethyl) pyridine at best at temperatures in the range of approximately 150 bar. Typical for an intermediate optimal range is the preferred range from about 155 to 145 ° C for the chlorination of 3,5 ~ dichloro ~ 2 ~ (trichloromethyl) pyrizum 5 * 5 # 6-trichloro-2- (trichloromethyl) pyridino

The reaction is preferably carried out in the presence of actinic radiation such as ultraviolet light. A light source emitting light with a wavelength of about 2000 to 5000 t, in particular from about 5000 to about 4000 Å, is suitable.

909808/1125

^ T,

is carried out in the presence of a light source, the Light source also serve as alo heat source. Commercially available Elevated suns are suitable for such use

The reaction is preferably carried out in the absence of a solvent or diluent carried out. Certain solvents or thinner can be used however, this usually has no practical value since good results can be obtained without using them. if a solvent or diluent is used, ao Attention should be paid to the type of solvent and its boiling point. So use low-boiling solvents Reaction temperatures down and would »if used cause an iterative reduction in the efficiency of the reaction or significant changes in equipment require solvents with reactive groups such as water could cause weaving reactions. Suitable solvents are chlorinated solvents such as hexachlorobutadiene. It should also be noted that better results are obtained when water, which is often added in some chlorination processes, can be strictly excluded will.

The speed of the chlorine flow and the total time of the Supply of the same will be in part by chemical and in part

909Ö08 / 1125

BAD ORiGS μ AL

due to mechanical requirements. Factors to be taken into account when determining the most favorable supply amount include the size and / or shape of the vessel, mechanical entrainment of the product in the exhaust gas, reaction temperature, mechanical aids for contact effectiveness, use of countercurrent, use of packed columns, single passage of Oae or recirculation and the like ο in general Good results can be obtained when the rate of the chlorine stream is from about 0.5 to about 5 Hol of chlorine per mole 2- (Trichloromethyl) -pyridln'-reaction component ^ e hour, but higher or lower rates can be used also with good success depending on the specific circumstances and conditions are used. The higher flow rates can sometimes lead to excessive reaction and Formation of by-products or they can lead to a physical entrainment of the product and loss of the same conditional in the Abzugstfasstrc3. Lower flow rates can reduce the reaction rate to such an extent that additional heating from the outside is required becomes necessary. It should be noted that the heat source partly an inner, i.e. reaction heat, and partly a kisser, i.e. Elevated and thermal radiation, is "

The total time of supply of chlorine gas is determined by the oesohumness of the chlorine flow, the total amount to be supplied

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~ 55 -

of chlorine, the temperature of the reaction and the like. The lower limit is of course the time required to introduce a stoichometric amount of chlorine into the reaction medium. The upper limit can vary depending on the applied for conducting the reaction special procedures and therefor applied special conditions vary _o If the reaction is carried out in a manner that is returned in the chlorine, the required amount of chlorine is the stöcho-Botrieohe Henge or a slight excess , since practically no chlorine is lost or consumed in side reactions under the temperature conditions given above. Under these conditions, the temperature required is that which is necessary for the consumption of the chlorine supplied. If the chlorine decomposition is carried out in a single pass of the chlorine, intimate contact of the chlorine with the 2- (trichloroethyl) pyride in-reaction component can be achieved by passing chlorine gas through the liquid reaction component until the reaction has practically ended. Under the temperature conditions preferred for carrying out the reaction, the addition of about a two-fold to about ten-fold molar excess is considered to be an expedient range. The practical completeness of the reaction can easily be determined by taking a sample from the reaction mixture and using known working methods, such as, for example, analysis by Daspfphiusenohroa & togr & phle. If the re-

909808/1125

Actlon temperatures aioh tier upper limit nKhern, should a very large excess of chlorine should be avoided Reduce side reactions to a minimum.

After the end of the reaction, scan the reaction image allow to cool to room temperature to recover the 6-chloro-2- (triohlomethyl) pyridine product as a solid. Preferably, the reaction mixture is distilled before cooling * in order to obtain a practically pure product. Possibly Further purification processes, such as fractional distillation and / or crystallization, can be used.

In a preferred modification of this embodiment of the Invention, the suitable 2- (trichloroethyl) ~ pyridine compound is irradiated by means of a suitable light source and to a temperature of about 110 to about 160 ° C heated, and chlorine gas is thrown through the heated Reaktlonskoapo «· nente in an amount from about 0.5 moles to about 5 moles per mole 2- {Triohlor »ethyl) pyridine compound passed through per hour until the reaction is practically complete. After this Over a period of time, the reaction mixture is distilled to obtain the desired product.

The following examples illustrate the invention without restricting it.

909808 / Π2 5

H45653

example 1

An operation was carried out in an apparatus that was called Prlirtrreaktlonegäas an oefltss of 17 1 capacity (A), • a water-cooled column with an internal diameter of 50 Bt (2 lnohea) and a length of 914 nsti (56 lnohes) (B) and a condenser (C), which consisted of a water-cooled column with a durometer of 50 mn (2 inches) and a lungs of 555 mm (14 inches).

The primary reactor was 27.2 kg (60 pounds) one mix partially chlorinated pioolin from a previous one Attempt sent as an initiator source. The temperature of the reacted reactor was then increased to 210 ° C, and gaseous chlorine was introduced in an amount of about 2.5 to 3 fc * (5 * 5 - 6.6 pounds) per hour. The gaseous Chlorine reacts with the partially chlorinated pioolin in the Initiator occupancy with formation of hydrogen chloride, the released from the oil and passed to the column (B) became. Pioolin was introduced into column (B) in an amount of about 0.5-0.55 kg (1.1-1.2 pounds) per hour. The pioolin introduced in this way came with the gaseous chlorinated water Substance la counter-atom in contact and reacted with this to form pioolin hydrochloride, which in the presence of excess gaseous hydrogen chloride formed a liquid pioolin hydrochloride mass, which down in the primary reaction

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58 - H45653

Gefäs3 arrived. The liquid pioolin hydrochloride mass thus continuously introduced into the chlorination medium in the principle reaction vessel reacted with the gaseous chlorine which was continuously introduced for 17 hours via a product mixture enriched in 6-chloro-2- (tr-iohlomethyl) pyridine to build. After reaching the stationary to "article, the Produktgemisoh with ainesi Hein visibility of about 80? I continuously d © ra Beaktionsgefäse was kg at a rate of about 1.3 (3 pounds) per hour without distillation entfemtj the product made about 22.7 kg (50 pounds) of "a crystallized Methylenehlorid-pentane sample of the product tries a melting point of 52.5 to 62.9 to C ^e. analysis

Calculated C 31.20 H 1.31 Cl 61.1 N 6.05 Found 31 * 23 1.32 61.22 5.99

Another sample recrystallized from pentane with a slightly lower melting point showed an infrared spectrum, atm practically old that of an authentic sample prepared by an independent synthesis, from 64 to 65 ° C, and a degree of purity of 98 ° in the case of ooriatographic analysis compared to the pure sample.

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BATH ORIGINAL

Example 2

Continuous chlorination was carried out in a manner similar to Example 1, but at 220 ° C as the reaction temperature. Over a period of 15 hours, 8.2 kg (18.1 pounds) (0.194 pound moles) of α-picoline were introduced, and after After a residence time of about 18 hours, a product enriched in 6-chloro-2- (trichloromethyl) pyridine was drawn off from the reactor without distillation in a yield of 20.6 kg (* 5 # * pounds). Upon cooling, the liquid solidified to a cream-colored calibration solid of F - 50 to 59 ^e C. The product contained about 75% flüohtige materials, of which, such as (Ue analysis showed duroh vapor phase chromatography, 90.8% of 6-chloro-2- ( triohlomethyl) pyridine This corresponds to 68 % 6-chloro-2- (trichloromethyl) pyridine in the product obtained.

Example 3

using the conditions described in Example 2 271 kg (597 pounds) of 6-chloro-2- (triohloreethyl) -pyrldine rich Oemlsoh was prepared.

4 g of the product thus obtained was used

a 2Q-b8digen, 2.5 ^ -om-Oldershaw-Column (1 inoh) fractionated at an RUokflussveratnis of 20: 1

distilled to obtain purified 2-chloro-6 «> (trlohlormethyi) - : * v:. ■: <: 909808/1125

H4S653

pyrldin "obtained with a Heinheitegrad 98.5 to 98.6% (by analysis by vapor phase chromatography) asu the VCN under a pressure 11 mn Hg 12 * bie 6 to IJT, 5 ^# C distilled and accounted for 52% of the Oesamtmateriale.

Example 4

In a similar operation, but using two-stage chlorination, picoline was obtained in an amount of 0.5 kg (1 pound) per hour and chlorine in an amount of approximately 1.8 kg (4 pounds) per hour placed in a chlorination tank exposed to old ultraviolet light with a reactor temperature of 190 °. After a residence time of 48 hours, sampling and analysis by vapor phase chromatography gave the volatile product 80 # 6-chloro-2- (trichloroethyl) -pyridine and 12 % 2- (trichlone-methyl) -pyridine. The product was then placed in a second "reaction vessel exposed to ultraviolet light" and chlorinated at 170 ° C. at the same temperature, 1.4 kg (^ pounds) of a product which was further based on 6-chloro-2 "(trichloromethyl ) pyridine was enriched and old volatile constituents 90 mol # 2-chloro-6- (triohlor- ■ ethyl) -pyrldln and 3 Hol £ 2- (Triehlonnethyl) -pyrldin contained, as was beatlraait by analysis by vapor phase ohroicatography

909808/1125

BATH ORIGINAL

Example 5

An operation was described in Example 1 Apparatus carried out.

The primary reaction vessel was charged with 1.45 kg (5.2 pounds) of a partially chlorinated picoline mixture from a previous seed as an initiator charge. The temperature of the charged reactor was then raised to 100 ° C and gaseous chlorine was introduced in an amount of about 4 kg (9 pounds) per hour. The gaseous chlorine reacted with the partially chlorinated pool in the initiator charge to form hydrogen chloride, which escaped from the gas and was introduced into column (B). Picoline was introduced into column (B) at a rate of 0.318 kg (0.7 pounds) per hour. The Picolin Icaa bit introduced in this way came into contact with the gaseous hydrogen chloride in countercurrent and reacted with it to form Pioolln hydrochloride, which in the presence of excess gaseous hydrogen chloride formed a liquid Pioolin hydrochloride mass, which passed downwards into the primary reactor. 227 g (0.5 pound) of aluminum chloride catalyst (about 1% by weight , based on the total picoline used) were introduced into the liquid pioolin hydrochloride mass which left column (B) and became with this in the Primarreaktlonsgeffiss

909808/1125

BATH

Gefcraoht, The liquid picoline hydrochloride mass, which was continuously introduced into the chlorination medium of the primary reaction vessel, reacted with gaseous chlorine, which was continuously introduced over a period of 72 hours, to produce an amount of 3,4,5,6-tetrachloro- ° 2 - »(trichlorom5ethyl ) - to form pyridine-rich product mixture. After the steady state was reached, the product was continuously removed from the primary reaction vessel. It weighed 59 kg (130 pounds). Analysis of the oils to .angereicherten ^ 4 _i 5 »6 ~ ~ 2 tetrachloride (trichloromethyl) pyridine product by vapor phase chromatography showed" that the mixture additionally 3 _J 4,5-Triohlor <'2- (triohlorinethyl) "> pyridine and 3 '^ I5-Triehlor ~ 2- (diohlorffiöthyl) -pyridine contained as the main coroponents. The composition of the product in mol # was the following: 30 % 3,4,5,6- * tetrachloro-2 ~ (triohlomethyl) -pyridine, 32 % 3 # ² ^ 5 "" trichloro-2- (triohlormethyl) -pyridln _# 16 % ^^, S-Triohlor ^ -CdichlormothylJ-pyridine, about 6 % 3,5-dichloro-2- (trichloroethyl) .pyridine, about 7 % 3,5 # 6 "Triohloi · 2- (trichlorotethyl) -pyridine and about 4 # 3,5- "Diehlor-2- (diehlorme thy1) -pyridine,

The components of the reaction mixture can easily be separated by fractional distillation.

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-43- 1U5653

Example 6

A reaction was carried out practically as in Example 1, old with the exception of the fact that the catalyst was introduced in the form of aluminum spines, with the aluminum being old The hydrogen chloride released in the primary reactor reacted with the formation of aluminum chloride in situ. Because of this Modified procedures were 32 moles £ 3,4,5,6-Tetraohlor-2- (triohloraethyl) -pyridin, 30 Hol * 3 *** 5-Triohlor-2- (t'riehloraethyl) -pyridin and 15 moles * 3 * * »5-triehlor-2- (dichloromethyl>. pyrldln received.

Example 7

A similar operation was carried out in which the following changes have been made; (a) Change of the Uhrungsgesohvlndigkelt from Hoolin to 250 g per hour, (b) Dark reaction, i.e. no ultraviolet light was applied, and (c) Change in the amount of catalyst used (2% by weight of aluminum, based on the weight of the used Picoline). The chlorination was carried out in the manner described above for 0 hours, a product mixture enriched in 3 * 4 * 5 * 6-tetrachloro-2- (trichloneethyl) pyridine being obtained, which was obtained continuously from the reaction vessel. Analysis of the product by Daapfphasenohroatatographie gave 29 mol £>, *, 5 »6 ~ Tetraohlor-2-

909908/1125

(trichloromethyl) -pyridine, 53 mol # 3,4, S-trlohloro-S- (trchloromethyl) -pyrldine and 15 mol # 5,4,5-triohloro-2- (dlohlonethyl) -pyridine.

Example 6

In a further step, a chlorination was carried out under irradiation, whereby ferric chloride catalyst, introduced as metallic iron in an amount of 1.5% by weight based on picoline was used. The reaction was described as before by introducing gaseous Chlorine in those with a partially chlorinated piolingealoh charged reactor and introduction of picoline into the column (B) at a rate of 250 g per hour during Performed 24 hours, with a highly chlorinated Product was obtained containing 29 moles of # 3,4,5,6-tetrachloro ~ 3- ■ (trichloCTsethyl) pyridine, 52 mol of 3 / 4,5-trichloro-2- (triohlor-B6thyl) -pyridine and 17 mol of # 5 # * # 5-trichloro-2- (diohlomethyl) pyridine.

Example 9

In another work course Pioolln was in the column (B) imported in an amount of 250 g per hour for 50 hours, Phosphorus penta chloride catalyst in the primary reaction vessel

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BATH ORIGINAL

in an amount of a total of £ 1, based on the total amount of pioolin used, and introduced gaseous chlorine into an irradiated mixture of initiator solution of partially chlorinated picolines in the primary reaction vessel for 30 hours, a product containing 30 % 3.4, S. 6 -tetrachloro-2- (trichloromethyl) -pyridine, 33 % 3,4,5-trichloro-2- (trichloro3thyl) -pyridine and 17 % 3,4,5-trichloro-2- (chloromethyl) -pyridine.

Example 10

- ^ - (trichloromethyl) -pyrldln

39 g (0.2 mol) of 2 - (? Riohlormethyl) pyridine were in a

• t

Tubular apparatus was introduced, and the reaction component was irradiated using a reflecting sun (type RS-4) and heated. As soon as the temperature of the reaction component was about 135 ° C., a stream of gaseous chlorine was emitted at a rate of about 0.45 mol per hour for 1.5 hours passed through to obtain the desired δ-chloro-2- (trichloromethyl) pyridine having a molecular weight of 231. · The Analysis of the product that 71 mol £ from 6-chloro-2- (triohlomethyl) pyridine and the Remainder consisted of unreacted starting material,

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⁴⁶ - H45653

Example 11

6 ~ chloro-2- (triohlormethyl) pyridine

Similarly WoIsS ₁ as described above, gaseous chlorine at a rate of about C, 5 mol per hour in 38.0 g (0.295 Hol) heated and irradiated 2- (trichloromethyl) pyridine would be conducted. The supply of the gaseous chlorine was continued for 7.5 hours while the temperature of the reaction temperature was maintained in the range of 120 to 1.55 ° C., the desired 6-chloro-2- (triohlomethyl) -pyridine being formed. After cooling the reaction mixture, the product crystallized as a solid from P 65 to 66 ° C. The infrared spectral analysis showed that the product with this melting point is pure 6-chloro-2- (triohloriiethyl) pyridine. The yield of the product was 64 g or 94 % of theory.

Example 12

5,6-dichloro-2- (triohlomethyl) pyridine

In Khnlioher Welse, a stream of gaseous chlorine was introduced in an amount of 0.4 mol per hour into 46 g (0.20 mol) of 2-chloro-2- (trichloromethyl) pyridine; which was irradiated and heated at a temperature of about 120 to 130 ^{9 C.} The dura- tion of chlorine was frozen away for about 5.75 hours, where-

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8AD ORIGINAL

when 48.4 g of crude 3,6-dichloro-2- (trioUlormethyl) pyridine were obtained. Analysis of the crude product by vapor phase chromatography showed that 79 * 6 £ consisted of the desired 3 _# 6-diehlor-2- (triohlorinethyl) pyridine. This corresponds to a theoretical yield of the desired product of 73 Jf. The product had a melting point of 47-48 ^s after recrystallization from hexane C.

Example 13 3.6 Dichloro-2- (triohloraethyl) "pyridine

In a similar way, 270 g of 3-chloro-2- (triohlonaethyl) -pyridine reaction component were irradiated with a sunlane and heated up, and a stroa gas-filled chlorine was in one Initiated amount of 0.45 mol per hour for 15 hours. During this period the temperature was in the range of 105 to 110 ° C held, with the reaction taking place and 249 g raw 3 »6-dichloro-2- (trichlonaethyl) -pyridine were formed. Analysis of the crude product by phaaenahroatography showed a conversion of the converted 3-chloro-2- (trichloromethyl) -pyridine into the desired product.

BAD LOCATION ¹ NAL 8/1125 ^BA

Example- 14 "

Similarly tialQe T ^ ere $ 6 g of 5-chloro-2- (trichlonaethyl) ■ pyrldix "is a Tsrasp ^ mttsrbereiea of 120 to 130 ° C by passing raw Burch chler» in an amount of 0.4 moles J © would during 2 , 5 StiHiden. chlorinated, crude 5 * 6-dichloro-2- (tri6hlorosaethyl) pyridine being obtained in a yield of 65 g. The desired product snaofete 6k ^ MaIfZ of Froduktgemisöhs &. \ M as r2urch Analy ** 'by' Dssspfphiisemchroniatographie bestimrat ifurde, 12nd obtained from your mixture duroh fractional distillation. The 5,6-dichloro-2- (triohlor «ket-hyl) -py2 * ldin formed a welaee crystalline F β 38 * C« · '

Balap lel 15

^ j5 | e-Trt.ohlor-a »(tr lofalerne thyl)

43 g (0.16 mol) of 5 _# 5 "Mohlor ~ 2" (trichlcnoethyl) -p3rrldin were chlorinated in a Khnllüfeer manner at a temperature in the range from 155 to 1 * 5 * C, where>_# 5 * 6-> trichlor -2- (triohlora »th3rl) -p3rridln was obtained. The conversion of converted 7 "54aofaIoi * -2 * (trlelilenMithyl) -pgrridln- <a 3,5,6-trichlor 2 - '{tFlohloxnetnyl) -F3rrXdin was 50 $ _o The product * urd«

SAO ORIGINAL

obtained by fractional distillation and wios a Boil pressure, inkfe boi a pressure of 1 rara He of 120 * C.

At room temperature, 3,5 # 6-trichloro is 2- (triohleriaethyl) ~ pyridine a white crystalline material from F «58 to 59 ° C

Example 16

-g «'(tri ohlo rmethyl) -pyridi n

Similarly, ¹ K) g (0,1? Üdl) 5 *** 5-trichloro-2- (triohlonnethyi) -pyridine were nit under irradiation and heating "of a sunlamp at et fa ^ 150 ^e C by Durohlelten of gaseous chlorine chlorinated in one mango of 0.5 mol per hour for 5 hours, the desired 3,4,5,6-tetrachloro-2- (trichlona3thyl) -pyridi «with a conversion of about 27 Ji of the converted 3» ^ # 5 - ^l triohlor-2- (trichloromethyl) pyridine was obtained.

3 # ^ * 5,6-Tetraohlor-2- (triohloraethyl) -pyridine is a white crystalline solid matter from P »58 to 60 ° C, It is in many organic solvents, such as carbon tetrachloride, Perchlorethylene, chloroform, diethyIKther and Pentane is loosely and practically insoluble in water.

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⁵⁰ "U45653

% ~ Chlorine ~, 3, ^ - BlShIoP * csder 4 _r 5 "Dichloro-2- (trichloroB" tiiyl) -pyridines can be chlorinated effectively in a manner corresponding to that used in Example 13 "by 4, 6-Diehlor-, 5,4,6-Trichlor · - or 4,5 # 6 aethyl) -pyrldin.

j the 6-chloro-2- (triohlorB »ethyl) pyridine

anthalton «are valuable as antifouling inhibitors a typical example of such a use 2- (triohlonethyl) »pyridine in an aqueous solution aittel gslöat, ma produce a soil treatment agent, the 1000 Qettiohtsteile Stiolcatoff and T Oewiohtstell 6-Chlor- 2 ~ (triohloraetk3rl) ~ pyridine contains. The Mittal can be seen as a rare «»

(eidejlresaing) dQngar / on rows of gepflanitera Ifeigi, which in Sandleea Lehaboden has a pH of 7.9 wKohst, in such quantities applied HRirden that nitrogen in a quantity of 112 kg / ha (100 pounds per aore). The floor is at 50 bla 100 sä (2 to 4 inches) of water during the Waohsturaafceit to achieve high yields of narcotic males.

The methods produced in accordance with the process of the invention Btptaohlorpioolin related Oeasisohe

or be separated into their main component for the ultimate use in additions or as auegartgesateri & llett for the manufacture of other desired products. This can be done with 3 * ^J f * i> »6-TetrÄOhlor-2- (trlohlor / ethyl) -pyridine

909808/1125 BAD original

fortified product with inert adjuvants for manufacture Especially pest and Uhkr & utbek & detergents are diluted. When used in this way, the product kit dispersing agent becomes oil-proof and dispersed in water to form a spray, those when applied to the leaves of beans, Sähwelnekraut (pigweed) and foot-tail plants a complete kill of diose plants. The product enriched in 5,4,5,6-Tetraahlor-2- {triohloreethyl) ~ pyridine can also be used to convert ^^ eSie-fetraohlor-a-CtrichlonaethylJ-pyridine or 3 # * # 5-Trichlor-2- (trichlori3othyl) -pyridine are distilled, which can be used separately in Selifidlingßbek & apfunga or weed control products.

Those according to those illustrated in Examples 10-16 Cathode-made products have numerous uses. They are for example as vlrksaae components at useful for the provision of agents which are suitable for agricultural purposes. They are also called Weedkillers or SohSdlingsbekHnipfungsalttel without further modification when used as a hematoelde, Fungicides, disinfectants, germicides, herbioids and Xneefctloide valuable. The usability of the 6-Chloz> -2- (trichloro · «thyl) -pyridine compounds as Neaatooide is outstanding the following typical designs as an example. Various separate aqueous compositions were made

909800/1125 ORIGINAL BATHROOM

52 - H45653

made one of the following ö-chloro-iJ-ftriehlonnethyl) -. pyrid in compounds contained * ö-chloro-ß-itrichloroethyl) -pyridine »3,6-DlohXor-2- (trichloriBethyl) - pyrid: Ln, 3,4,5,6-Tetraohlor-2- (triühloOTethyl) - pyridine and 3,5,6-triohlor-2- (triehlorniethyl) * - pyrldln. These compositions were in separate sessions for 6 days at about 27 * C (80 * F) with larvae of WortIknollezmematodcn (rootknot nematode) in Brought in contact and yielded a complete in every case Control of the nematode larvae »

Certain of the 6-chloro2- (triochloromethyl) pyridine compounds have outstanding anti-chemical properties. In separate operations, for example, 5,6-dichloro-2- (trichloromethyl) -pyridine and 3,6-dichloro-2- (trichloromethyl) -pyrldine were dispersed in Mali-Hflf β-agar medium to form culture media Split out the elno of the 6 "chloro-2- (trlohlonnethyl) -pyridine compounds in a concentration of 100 parts by weight each Killion contained. The media were separately inoculated with Pullularia pullulan * and Candida pellloulosa and inoculated for 3 days incubated at 30 ° C. At this time, complete inhibition of the growth of the organisms was observed.

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Some of the 6-chloro-2 (trichloroethyl) pyridiny compounds are valuable as insectioids. In beiepielswelsen separate ArbeitsgHngen a 100 £ strength Abtutung was lie of Hauef and American KUohensoh & ersielt ben when the - se with compositions were brought into contact, the 500 (kmlohteteile ppm of 6-chloro-2 ~ (trichloroethyl) contained -PTTidin.

909808/1125

Claims (1)

U45653 Claims (Jj Process for the preparation of 2- (trichloromethyl) pyridines, which contain one or more chlorine substances on the core, by chlorination of α-fleolin or its chlorination products with chlorine at elevated temperatures, characterized in that chlorine is added to the 6- 3 division of the nucleus by chlorination of an S-C trichloroethyl / pyridine starting material or sulfuric product under conditions which enable or promote the removal of HCl from the (trichloroethyl) pyridine starting material or intermediate product. 2, method according to claim 1, characterized in that chlorination is carried out under such conditions that HCl is obtained from α-picoline or from 2- (mono- or 2- (dichloromethyl) -pyridines, which are in the Heaktionagemlsoh are present, not be removed. 3), method according to claim 1 or 2, characterized in that that the chlorination is carried out in the liquid phase. 4. The method according to any one of claims i to 3 ,. characterized in that the chlorine is used in its gaa-grained state. 909808/1125 5. The method according to claim h, characterized in that the removal of HCl from the 2- (triohlonaethyl) pyridine is promoted by passing an excess of gaseous chlorine through the 2- (triohlonethyl) pyridine-containing reactant. 6. The method according to any one of claims 1 to 5 *, characterized in that the removal of HCl from the 2- (trichloroethyl) pyridine effects or promotes by the Chlorination in the 6-position of 2- (triohlomethyl) pyridine carried out under practically anhydrous conditions. 7. The method naoh one of claims 1 to 6, characterized in that the removal of HCl from the 2- (TrI-ohlorm «thyl) pyridine causes or promotes by nan dl · Chlorination in the 6-position of 2- (triohloraethyl) pyridine at high temperatures. 8. The method naoh one of claims 1 to 7 »characterized in that the chlorination in the 6-position of the 2- (TriohlorMfchyl) -pyridines in the presence of actinic or performing ultraviolet light. 9 «Method according to one of claims 1 to 8, daduroh gainran · shows that the chlorination is carried out in the 6-6 position in Ο · β · η-wart of an inert solvent. 909808/1125 AiJ 10. The method smell one of claims 1 to 9, characterized in that daae nan α-picoline ver » turns. 11 ο Method according to claim 10, characterized in that ami the α-pioolin before carrying out the chlorination with HCl aKttlgt. 12. The method according to claim 11, characterized in that ταεη the saturation of the a-Pioolin rait HCl at a temperature of 20 to 70 ^e C carries out. Vß. Process according to one of Claims 10 to 12, characterized in that the side chain of the α-pioolin is chlorinated with little or no substitution in the 3- # ^ and / or 5 "segments of the core. 14. The method according to any one of claims 1 to 9, daduroh gekonnaRiclinet, that 2- (triohlor: aethyl) -pyridine or a 2- (Ti »ichloriBethyl) -pyr ^> idin-containing reaction mixture is used as starting material. 15. The method according to claim 1 * 1, characterized in that g <9kenn7eiohnet, daee xan daa 2- (prichloniethyl) «- pyridine is chlorinated at a temperature above about 1.5 * C. 8/1125 BATH ORIGINAL .57 1U5653 16. The method according to claim 14 and 15 «characterized in that the 2« (frichloromethyl) pyrldine is chlorinated at a temperature in the Dareich of 135 to 180 ° C under practically water-based conditions. 17 · The method according to any one of claims 10 to 14, characterized characterized in that the chlorination of a-Ploollns or 2- (Triohlom »thyl) -pyridin3 at a temperature above the Boiling point of any aqueous CC1> which can be formed or present in the reaction mixture. 18. The method according to claim 17 *, characterized in that that the chlorination of a-picoline or 2- (trichloromethyl) < pyridine at a temperature of 180 "C and optionally in a practically anhydrous system. 19. The method according to a derißna prtiche 17 or 18, characterized in that the chlorination of the ο-picolin or 2- (triohloreethyl) pyridine at a / temperature in the range from 180 to 230 ^e C is carried out. 20. The method according to any one of claims 17 to 19, daduroh characterized that the · «to the chlorination of a-picoline or 2- (trichloromethyl) -pyridine at a temperature in the range of 190 to 210 * C. 909808/1125 bath 21. The method according to one of claims 14 to 20, characterized in that gaseous chlorine is used in a hexagon of 1 to 2 weight per 1 weight per cent of a-pieoline or α-piooline saturated with HG1. 22. The method according to any one of claims 1 to 9, characterized in that that the> ■ ** ^ - and 5-positions of the kernel d «s a ~ picolins before the effect of complete chlorine substitution chlorinated in the ethyl group of a-Picolina. 22. The method according to claim 22, characterized in that "the chlorination of the a-Plcolin is carried out at a temperature in the range from 90 to 120 ^e C" 2. Process according to claim 22 or 23, characterized in that the chlorination of the α-picolina is carried out at a temperature in the range from 95 to 105 * 0. 25. The method according to one of claims 22 to 2.K _9, characterized in that gaseous chlorine is used in the chlorination of the a-pioolin in an amount of 11.5 to 21.5 parts by weight per 1 part by weight of a-pioolin · 909808/1125 26. The method according to any one of claims 22 to 25 »thereby characterized in that the chlorination of the a-pioolin in Performs in the presence of a catalyst. 27. The method according to claim 26, characterized in that nan uses a Lewis acid as a catalyst. 28. The method according to claim 26 or 27 *, characterized in that that the catalyst used is AlCl ,, FeCl, or FCl. 29 · The method according to any one of claims 26 to 28, characterized characterized that the catalyst is used in an amount of not more than 5 Ge * u-Ji, based on the weight of the a-Picolln, used. 30. The method according to any one of claims 26 to 29, daduroh ge »indicates that the catalyst in an amount of 0.5 to 1 Qew.- £, based on the weight of the α-PiColine, used. 31. The method according to any one of claims 10 to 30, daduroh characterized that the chlorination in continuous catfish, by continuous imports of the α-picolines and dos chlorine in a reaction vessel and continuously withdrawing the chlorinated picolines. 909803/1125 -60- "U45653 32 «, mistake" ® "according to one of the claims 1 to 9, thereby germinating the nozzle mm as an excipient 2- (trlohlorioethyl) pyridines containing 1 to 3 chlorine atoms in the 3- * * - and / or f> - £ ft®llun £ @ ii dee Kerns b® sit scm » 33. The method according to Anspn ^ h ^ 2 _£, characterized in that the carbon substitution in the 6-Stelluing by chlorination represents in the nucleus fsubstituierfcen 2 »(triochlorophyl) pyridines in the office from 11 ° to 16O * C. Jk _o method according to claim 32 or J55 # characterized in that one ImI d © r chlorination of these 2- (Triohloriaethy3) -. I ^ nridlne ge.afKnaig ^ »Qilor used in an amount of 0.5 to 5 moles per mole of 2« {Ts * iohlotTaethyl) »pyridine-ReÄktioneleoeponente, 55, method according to one of claims 32 to 34 _s characterized thereby, öaee neon ale AuegangaEiatarittl 3-chloro-2- (trichlorassthyl) -pyri & in used. 36 ,. Method according to claim 35, characterized in that daae the chlorine depletion in the 6-position de »3-chloro» 2- (trlcHloratthyl) -pyridine causes lnjea one oils chlorination the same area ainer Taasperttur ia I3e3roiöh from 110 to 120 ° C performs. 309808/1125 BATH ORIGINAL 37. Method naoh one of claims 32 to 34, characterized marked that men use 5-chloro-2- (trichloromethyl) -pyridln used. 38. The method according to claim 37, characterized in that. that atn causes the chlorine substitution in the 6-position of the 5-chloro-2- (trlohlornethyl)> pyrldlna, Inden one carries out the chlorination of the same at a temperature Ib range from 120 to 130 ° C. 39. Method according to one of claims 32 to 34, thereby characterized in that n & n uses 3,5-diohlor-2- (triohlormothyl) -pyridine as starting material, 40. The method n ^ oh claim 39 »characterized in that The chlorosubatitutlon in the 6 ~ position of the 3,5-dichloro-2- (trichloromethyl) -pyridine causes the Chlorination of the same at a temperature range from 135 to 145 * C pass through, 41. Method naoh one of claims 32 to 34, characterized characterized that «an ala, Auagangwnaterial uses 2,4,5-trichloro-2- (trichloroethyl) -pyridine. 909808 / 112B _A method according to claim 41, characterized in that the chlorine substitution in the 6-position of the 3 * 4,5- = trichloro »2 ~ (trichl.orm3thyl) pyridine is effected by chlorination of the same at a temperature in Range from 150 to 160 ⁰ C 'carried out. 45ο Fertilizers, characterized by a content of organic and / or reduced nitrogen "preferably in the form of Armonlak: or Arcraoniuinionen, and additionally 6-chloro-2- (trichloromethyl) -pyridine as an agent for the control of the soil" nitriflcatlon. " 44 “Method for creating an improved soil as Growth mediura, the organic and / or reduced nitrogen and in particular contains nitrogen in the form of ammonia or ammonium ions, characterized in that in the bottom 6 ~ chloro-2- (trichloromethyl) ~ pyridine and an organic and / or introduces fertilizer containing reduced nitrogen ,. 909808/1125