KR101894778B1

KR101894778B1 - Method for preparing alkyl halides

Info

Publication number: KR101894778B1
Application number: KR1020170030695A
Authority: KR
Inventors: 허남회; 이병노; 이규형
Original assignee: 서강대학교산학협력단
Priority date: 2016-03-11
Filing date: 2017-03-10
Publication date: 2018-09-04
Also published as: KR20170106241A; WO2017155356A1

Abstract

The present invention relates to a process for preparing an alkyl halide using hydrazine derivatives under solventless conditions, which simplifies the production process, requires no additional solvent, is economically advantageous, and can produce alkyl halides with high yields.

Description

METHOD FOR PREPARING ALKYL HALIDES < RTI ID = 0.0 >

The present invention relates to a process for the production of halogenated hydrocarbons using hydrazine derivatives under solventless conditions.

Many kinds of alkyl iodides are known and widely used in organic reactions. Among them, methyl iodide (CH ₃ I) is the most widely used alkyl iodide substance. For example, in the Monsanto process for producing acetic acid, alkyl iodide is used as a catalyst for the methanol carbonylation reaction . The alkyl iodide is also used as an effective methylating material in organic metal compound synthesis and organic chemical reaction. Methyl iodide is also a potential material that can be used to prepare saturated or unsaturated hydrocarbons with higher numbers of carbons as intermediates. Studies on the synthesis of methyl iodide have been carried out variously as reported in U.S. Patent 4,302,432, U.S. Patent 3,053,910, and U.S. Patent 4,731,494. In particular, methods for obtaining methyl iodide directly from hydrocarbons, such as U.S. Patent No. 4,731,494, are also disclosed but are difficult to commercialize due to their low yield. In addition, Gorin et al. Proposed a method for making methyl iodide through chlorination of methane with copper chloride, potassium chloride, and HCl (Ind. Eng. Chem., 1984, 40, 2128-2134) . In the case of U.S. Pat. No. 4,523,040, methyl halide was synthesized directly from methane under a solid acid or a metal catalyst by halogenation using chlorine or bromine. Thus, although methods for synthesizing methyl iodide directly from methane have been proposed, there has been no successful synthesis of methyl iodide. In addition, M.-M. Garza-Suarez et al. Reported the synthesis of methyl iodide from methyl alcohol using iodine and sponge iron as catalysts (Ind. Eng. Chem. Res., 2001, 40, 5675- 5679).

Accordingly, the present invention is directed to a process for preparing an alkyl halide comprising reacting a hydrazine derivative, an alcohol, and a halogen under solventless conditions.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

The first aspect of the present invention includes a process for producing a halogenated hydrocarbon represented by RX by reacting a hydrazine derivative, an alcohol represented by ROH, and a halogen represented by X ₂ under solventless conditions, &Lt; / RTI > wherein R < 1 >

[Chemical Formula 1]

In Formula 1,

R ₁ , R ₂ and R ₃ are each independently H; Or a substituted or unsubstituted C _1-30 aliphatic hydrocarbon group, a substituted or unsubstituted C _3-30 aliphatic cyclic group, a substituted or unsubstituted C _3-30 hetero aliphatic cyclic group, a substituted or unsubstituted C _{A 5-30} aromatic ring group, and a substituted or unsubstituted C _5-30 heteroaromatic ring group.

The halogenated hydrocarbon manufacturing method according to embodiments of the present invention can synthesize a halogenated hydrocarbon without using a solvent and a catalyst, so that no additional solvent or catalyst separation is required. Therefore, the separation process for separating the product and the reactant in the entire process can be minimized, and the process can be simply performed. In addition, halogenated hydrocarbons can be obtained from the reactants at a yield and conversion of about 98% or higher, and no additional solvent is required, which is economical advantage.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

In the specification of the present application, "aliphatic (aliphatic) hydrocarbon group" means a saturated or unsaturated hydrocarbon group containing 1 to 30 carbon atoms, and for example, C _1-30 alkyl, C _2-30 alkenyl group, or C _{2- 30} alkynyl group, and the like, but the present invention is not limited thereto.

Throughout this specification, the term " alkyl group " refers to an alkyl group having from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20 carbon atoms, from 1 to 15 carbon atoms, An alkyl group having from 1 to 10 carbon atoms, from 1 to 8 carbon atoms, from 1 to 5 carbon atoms, from 1 to 3 carbon atoms, from 3 to 8 carbon atoms, or from 3 to 5 carbon atoms Substituted or unsubstituted linear or branched alkyl groups having from 1 to 5 carbon atoms. For example, the methyl group is in the group, ethyl group, n- propyl group ⁽ⁿ Pr), iso- propyl ⁽ⁱ Pr), n- butyl group ⁽ⁿ Bu), tert- butyl ^(t Bu), iso- butyl ⁽ⁱ Bu), sec- butyl ^(s Bu), pentyl, hexyl, iso-hexyl, heptyl, 4,4-dimethyl pentyl, octyl, 2,2,4-trimethyl pentyl group, Nonyl group, decyl group, undecyl group, dodecyl group, isomers thereof, and the like, but the present invention is not limited thereto.

As used throughout this application, an "alkenyl group" refers to a linear or branched, substituted or unsubstituted alkyl group having from 2 to 30, from 2 to 25, from 2 to 20, from 2 to 15, from 2 to 10, An isopropenyl group, an isobutenyl group, an isobutenyl group, a t-butenyl group, an n-pentenyl group, or an n-hexenyl group, and the like, or an unsaturated hydrocarbon group such as an isopropenyl group, But are not limited thereto.

As used throughout this application, an "alkynyl group" refers to a linear or branched, substituted or unsubstituted alkyl group having from 2 to 30, from 2 to 25, from 2 to 20, from 2 to 15, from 2 to 10, Unsaturated hydrocarbon group and may include, but not limited to, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, or a decynyl group.

Throughout the specification of the present application, an "aliphatic ring group" means an unsaturated or saturated carbon of 3 to 30, 3 to 25, 3 to 20, 3 to 15, 3 to 10, 3 to 8, or 3 to 6 carbon atoms And may be, for example, a cycloalkyl group, a cycloalkenyl group, or the like of the hydrocarbon, but may not be limited thereto.

As used throughout the specification, the "cycloalkyl group" means a substituted or unsubstituted hydrocarbon ring group having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 20 carbon atoms, 3 to 15 carbon atoms, 3 to 10 carbon atoms, 3 to 8 carbon atoms, And includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group and the like.

Throughout this specification, the term "halogen" or "halo" refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

Throughout the specification, the term "aromatic ring group" means a C _5-30 aromatic hydrocarbon ring group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a phenanthrenyl group, Means an aromatic ring such as a perylenyl group, a chrysenyl group, a fluoranthenyl group, a benzofluorenyl group, a benzotriphenylenyl group, a benzocyclenyl group, an anthracenyl group, a stilbenyl group and a pyrenyl group Quot; aromatic heterocycle " means an aromatic ring containing at least one heteroatom, for example, a pyrrolyl group, a pyrazinyl group, a pyridinyl group, an indolyl group, an isoindolyl group, a furyl group, a benzofuranyl group, A benzothiophenyl group, a dibenzothiophenyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a carbazolyl group, a phenanthridinyl group, an acridinyl group, a phenanthrolinyl group, a thienyl group, a pyridine ring , A pyrazine ring, a pyrimidine A pyrrolidine ring, a dioxane ring, a piperidine ring, a morpholine ring, a piperazine ring, a carbazole ring, a furan ring, a pyrrolidine ring, a pyrazine ring, a pyrazine ring, a triazine ring, an indole ring, a quinoline ring, an acridine ring, A thiadiazole ring, a thiadiazole ring, a triazole ring, an imidazole ring, a benzimidazole ring, a pyran ring, and a di Quot; means an aromatic heterocyclic group formed from a benzofuran ring.

Hereinafter, embodiments of the present invention are described in detail, but the present invention is not limited thereto.

[Chemical Formula 1]

In Formula 1,

In one embodiment of the present invention, the C _1-30 aliphatic hydrocarbon group, the C _3-30 aliphatic cyclic group, the C _3-30 hetero aliphatic cyclic group, and the C _5-30 hetero aromatic cyclic group are each a Si, O But is not limited to, at least one element selected from the group consisting of S, Se, N, P, As, F, Cl,

In one embodiment of the invention, the hydrazine derivative may be in a solid state at room temperature.

In one embodiment of the present invention, the aliphatic hydrocarbon group represented by R ₁ , R _2, and R ₃ in Formula 1 means a linear or branched saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms. For example, , C _1-30 alkyl, C _1-25 alkyl, C _1-20 alkyl, C _1-15 alkyl, C _1- ₁₀ alkyl groups, C _1- ₈ alkyl, or C _1- ₆ alkyl group; C _2-30 alkenyl group, C _2-25 alkenyl group, C _2-20 alkenyl group, C _2-15 alkenyl group, C _2-10 alkenyl group, C _2-8 alkenyl group, or C _2-6 alkenyl group; C _2-30 alkynyl group, a C _2-25 alkynyl group, a C _2-20 alkynyl group, a C _2-15 alkynyl group, a C _2-10 alkynyl group, C _2-8 alkynyl, or C _2-6 alkynyl group But are not limited thereto. For example, the aliphatic hydrocarbon group may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, But are not limited to, methyl, ethyl, n-butyl, hexyl, and all possible isomers thereof.

In one embodiment of the present invention, in Formula 1, the aliphatic cyclic group described for R ₁ , R ₂ , and R ₃ has 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 20 carbon atoms, 3 to 15 carbon atoms, , 3 to 8, or 3 to 6 carbon atoms, and may include, for example, a cycloalkyl group or a cycloalkenyl group, but it is not limited thereto. The cycloalkyl group means a substituted or unsubstituted hydrocarbon ring group having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 20 carbon atoms, 3 to 15 carbon atoms, 3 to 10 carbon atoms, 3 to 8 carbon atoms, or 3 to 6 carbon atoms, But are not limited to, methyl, ethyl, propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and all possible isomers thereof.

In one embodiment of the present invention, in Formula 1, the aromatic ring group described for R ₁ , R _2, and R ₃ is a C _5-30 aromatic hydrocarbon ring group, a C _5-25 aromatic hydrocarbon ring group, C _5-20 aromatic hydrocarbon ring group, C _5-16 aromatic hydrocarbon ring group, C _5-14 aromatic hydrocarbon ring group, C _5-12 aromatic hydrocarbon ring group, C _6-30 aromatic hydrocarbon ring group, a C _6-25 aromatic hydrocarbon ring group, an aromatic hydrocarbon ring group, a C _6-20 aromatic hydrocarbon ring group of a C _6-16 aromatic hydrocarbon ring group of C _6-14, or an aromatic hydrocarbon ring of C _6-12 But are not limited thereto. For example, the aromatic ring group may be selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, phenanthrenyl, triphenylenyl, perylenyl, But are not limited to, aromatic ring groups such as a benzotriphenylenyl group, a benzocyclenyl group, an anthracenyl group, a stilbenyl group, and a pyrenyl group, and isomers thereof.

In one embodiment of the present invention, the aromatic heterocycle described above for R ₁ , R _2, and R ₃ in Formula 1 is an aromatic ring containing at least one heteroatom and includes C _5-30 aromatic hetero ring group, a C _5-25 aromatic heterocyclic group, the C _5-20 aromatic heterocyclic group, the C _5-16 aromatic heterocyclic group, the C _5-14 aromatic heterocyclic group, the C _5-12 aromatic hydrocarbon ring ring group, a C _6-30 aromatic heterocyclic group, the C _6-25 aromatic heterocyclic group, the C _6-20 aromatic heterocyclic group, an aromatic heterocyclic group, the C _6-14 aromatic hydrocarbon ring of C _6-16 A cyclic group, or a C _6-12 aromatic heterocyclic group. For example, the aromatic heterocyclic group may be a pyrrolyl group, a pyridinyl group, a pyridinyl group, an indolyl group, an isoindolyl group, a furyl group, a benzofuranyl group, an isobenzofuranyl group, a dibenzothiophenyl group, A thienyl group, a pyranyl ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrolidine ring, a pyrrolidine ring, a pyrrolidine ring, A heterocyclic ring, a piperazine ring, a carbazole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrolidine ring, a pyrrolidine ring, Aromatic heterocycle formed from an oxadiazole ring, a benzoxazole ring, a thiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzoimidazole ring, a pyran ring, or a dibenzofuran ring ring It is meant to include.

In one embodiment herein, the hydrazine derivative may comprise NH ₃ NHCO ₂ .

In one embodiment of the invention, the alcohol may be a linear or branched C _1-10 alcohol, or a cyclic C _3-10 alcohol.

In one embodiment herein, the linear or branched C _1-10 alcohol has from about 1 to about 10 carbon atoms, from about 1 to about 8, from about 1 to about 6, from about 1 to about 5, from about 1 to about 4 , Or from about 1 to about 3, linear or branched alcohols, but is not limited thereto. For example, the linear or branched C _1-10 alcohol may be selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, neo-butanol, , neo-pentanol, hexanol, and combinations thereof.

In one embodiment herein, the cyclic C ₃ -10 alcohols may be cyclic alcohols having from about 3 to about 10 carbon atoms, from about 3 to about 8, from about 3 to about 6, or from about 3 to 5 , But is not limited thereto. For example, the cyclic C _{3 -10} alcohols may include, but are not limited to, those selected from cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, and combinations thereof have.

In one embodiment of the invention, the halogenated hydrocarbon may be a linear or branched C _1-10 alkyl halide, or a cyclic C _3-10 cycloalkyl halide, wherein the halogen is F, Cl, Br , Or I.

In one embodiment herein, the linear or branched C _1-10 halogenated hydrocarbon has from about 1 to about 10 carbon atoms, from about 1 to about 8, from about 1 to about 6, from about 1 to about 5, from about 1 to about 4, or from about 1 to about 3, linear or branched alkyl halides. For example, the linear or branched C _1-10 halogenated hydrocarbon may be a methyl halide, an ethyl halide, an n-propyl halide, an isopropyl halide, an n-butyl halide, an isobutyl halide, a neo- But are not limited to, those selected from the group consisting of pentyl halide, isopentyl halide, neo pentyl halide, hexyl halide, and combinations thereof.

In one embodiment herein, the cyclic C _3-10 halogenated hydrocarbon is a cyclic cycloalkyl halide having from about 3 to about 10 carbon atoms, from about 3 to about 8, from about 3 to about 6, or from about 3 to about 5 carbon atoms But is not limited thereto. For example, the cyclic C _3-10 halogenated hydrocarbon may include those selected from the group consisting of cyclopropyl halide, cyclobutyl halide, cyclopentyl halide, cyclohexyl halide, and combinations thereof, .

In one embodiment of the invention, the halogenated hydrocarbon is selected from the group consisting of methyl iodide, ethyl iodide, propyl iodide, 1-iodo-2-methylpropane, 2-iodopropane, butyl iodide, 1- 2-iodohexane, 3-iodohexane, 3-iodohexane, iodocyclohexane, 3-iodo, 2,2-dimethyl Butane, or 2-iodo-2-methylpropane.

In one embodiment of the invention, for example, the halogenated hydrocarbon may be prepared by a one-step process such as, but not limited to, the following scheme:

[Reaction Scheme 1]

_{4ROH (l) + NH 3 NHCO} 2 (s) + 2X 2 (s) → 4RX + 4H 2 O + N 2 + CO 2

In the above Reaction Scheme 1, R is a C _1-10 alkyl group or a C _3-20 cycloalkyl group, and X is halogen, F, Cl, Br or I. For example, the C _1-10 alkyl group may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a neo- , neopentyl group, hexyl group, and all possible isomers thereof. For example, the C _3-20 cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, Isomers.

In one embodiment of the present invention, with reference to Reaction Scheme 1, a hydrazine derivative in a solid state can react with a halogen to produce hydrogen halide. The resulting hydrogen halide is reacted with an alcohol to obtain the desired halogenated hydrocarbon in the present invention.

According to one embodiment of the present invention, the halogenated hydrocarbon can be obtained in a yield of about 98% or more, about 99% or more, or about 100%.

According to one embodiment of the present invention, in the method for producing the halogenated hydrocarbon, the alcohol can be converted to the halogenated hydrocarbon at a conversion rate of about 98% or more, about 99% or more, or about 100%.

In one embodiment herein, the reaction may be carried out at a temperature above the boiling point of the alcohol, for example, at a temperature from about 80 C to about 200 C, and the upper limit of the reaction temperature depends on the type of alcohol used, May vary depending on the number of carbon atoms in the alcohol, but may not be limited thereto. For example, the reaction may be carried out at a temperature above the boiling point of the alcohol used, such as from about 80 ° C to about 200 ° C, from about 80 ° C to about 180 ° C, from about 80 ° C to about 160 ° C, From about 100 캜 to about 120 캜, from about 80 캜 to about 100 캜, from about 100 캜 to about 200 캜, from about 100 캜 to about 180 캜, from about 100 캜 to about 160 캜, About 120 ° C to about 200 ° C, about 120 ° C to about 180 ° C, about 120 ° C to about 160 ° C, about 120 ° C to about 140 ° C, At a temperature in the range of from about 140 ° C to about 160 ° C, from about 160 ° C to about 200 ° C, from about 160 ° C to about 180 ° C, or from about 180 ° C to about 200 ° C. If the reaction is carried out at a temperature below about 80 ° C, the conversion of the alcohol to the halogenated hydrocarbon may be reduced and if the reaction is carried out at a temperature above about 200 ° C, side reactions may occur and the selectivity of the halogenated hydrocarbons May be reduced, but may not be limited thereto.

In one embodiment herein, the reaction may be conducted for a period of time ranging from about 5 hours to about 12 hours, but may not be limited thereto. From about 5 hours to about 8 hours, from about 5 hours to about 12 hours, from about 5 hours to about 11 hours, from about 5 hours to about 10 hours, from about 5 hours to about 9 hours, from about 5 hours to about 8 hours, About 6 hours to about 9 hours, about 6 hours to about 8 hours, about 6 hours to about 10 hours, about 6 hours to about 9 hours, about 6 hours to about 8 hours, , About 6 hours to about 7 hours, about 7 hours to about 12 hours, about 7 hours to about 11 hours, about 7 hours to about 10 hours, about 7 hours to about 9 hours, about 7 hours to about 8 hours, From about 8 hours to about 12 hours, from about 8 hours to about 11 hours, from about 8 hours to about 10 hours, from about 8 hours to about 9 hours, from about 10 hours to about 12 hours, from about 10 hours to about 11 hours, For about 12 hours to about 12 hours. If the reaction proceeds for less than about 5 hours, the conversion of the alcohol to the halogenated hydrocarbon may be reduced, and if the reaction proceeds for about 12 hours, side reactions may occur to reduce the selectivity of the halogenated hydrocarbon , But may not be limited thereto.

In one embodiment of the invention, the reaction may be carried out under non-catalytic conditions.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following Examples.

[ Example ]

One. methyl Iodide synthesis

Example One

Of 0.64 g (20 mmol) under solvent-free conditions in methanol, 0.38 g (5 mmol) ₃ NH ₂ NHCO, And 2.54 g (10 mmol) of I ₂ were placed in a 20 mL vial, placed in a pressure reactor, and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example One:

Was carried out in the same manner as in Example 1 in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Example 2:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 2.5 mmol and 5 mmol, respectively, in the same manner as in Example 1. The mixture was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 1 were obtained.

Example 3:

NH ₃ NHCO ₂ under non-solvent conditions I < ₂ > was reduced to 1.25 mmol and 2.5 mmol respectively, respectively. The mixture was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 1 were obtained.

Example 4:

The procedure of Example 1 was repeated except that the reaction was carried out in an oven at 100 ° C for 12 hours under no-solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 1 were obtained.

Example 5:

The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out in a 100 ° C oven under no solvent condition for 6 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 1 were obtained.

2. Ethyl Iodide synthesis

Example 6:

Then under solvent-free conditions into the iodine of 0.92 g NH ₃ NHCO _2, and 2.54 g (10 mmol) of ethanol, 0.38 g (5 mmol) of (20 mmol) in 20 mL vial was placed in a pressure reactor, 100 Gt; C < / RTI > oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 2:

The same procedure as in Example 6 was carried out in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 7:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 2.5 mmol and 5 mmol, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 6 were obtained.

Example 8 :

NH ₃ NHCO ₂ under non-solvent conditions I < ₂ > was reduced to 1.25 mmol and 2.5 mmol respectively, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 6 were obtained.

Example 9:

The reaction was carried out in the same manner as in Example 6, except that the reaction was carried out in a 100 ° C oven under no solvent condition for 12 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 6 were obtained.

Example 10:

The reaction was conducted in the same manner as in Example 6, except that the reaction was carried out in an oven at 100 ° C for 6 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 6 were obtained.

3. Butyl Iodide synthesis

Example 11:

Then under solvent-free conditions into the iodine of 1.48 g NH ₃ NHCO _2, and 2.54 g (10 mmol) of butanol, 0.38 g (5 mmol) of (20 mmol) in 20 mL vial was placed in a pressure reactor, 100 Lt; 0 > C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 3:

The reaction was carried out in the same manner as in Example 11 in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 12:

Under non-solvent conditions NH₃NHCO₂WowI₂Was reduced to 2.5 mmol and 5 mmol, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product^OneH and¹³C NMR, and the same results as in Example 11 were obtained.

Example 13:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 1.25 mmol and 2.5 mmol respectively, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 11 were obtained.

Example 14:

The reaction was carried out in the same manner as in Example 11 except that the reaction was carried out in an oven at 100 ° C for 12 hours under no solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 11 were obtained.

Example 15:

The procedure of Example 11 was repeated, except that the reaction was carried out in a 100 ° C oven under no-solvent condition for 6 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 11 were obtained.

4. 1- Iodopentane synthesis

Example 16:

Then under solvent-free conditions into the iodine of 1.76 g butanol, 0.38 g (5 mmol) of NH ₃ NHCO _2, and 2.54 g (10 mmol) of (20 mmol) in 20 mL vial was placed in a pressure reactor, And reacted at 100 ° C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 4:

The reaction was carried out in the same manner as in Example 16 in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 17:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 2.5 mmol and 5 mmol, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 16 were obtained.

Example 18:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 1.25 mmol and 2.5 mmol respectively, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 16 were obtained.

Example 19:

The reaction was carried out in the same manner as in Example 16, except that the reaction was carried out in an oven at 100 ° C for 12 hours under no solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 16 were obtained.

Example 20:

The reaction was carried out in an oven at 100 ° C for 6 hours under no-solvent conditions, and the same procedure as in Example 16 was conducted. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 16 were obtained.

5. 2- Iodopentane synthesis

Example 21:

Then under solvent-free conditions into the iodine of 1.76 g (20 mmol) 2- pentanol, 0.38 g (5 mmol) of NH ₃ NHCO _2, and 2.54 g (10 mmol) in 20 mL vials, it is located in the pressure reactor And reacted at 100 DEG C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 5:

The reaction was carried out in the same manner as in Example 21 in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 22:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 2.5 mmol and 5 mmol, respectively, in the same manner as in Example 21. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 21 were obtained.

Example 23:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 1.25 mmol and 2.5 mmol, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 21 were obtained.

Example 24:

The reaction was carried out in the same manner as in Example 21, except that the reaction was conducted in an oven at 100 ° C for 12 hours under no solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 21 were obtained.

Example 25:

The procedure of Example 21 was repeated, except that the reaction was conducted in an oven at 100 ° C for 6 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 21 were obtained.

6. 1- Iodohexane synthesis

Example 26:

Then under solvent-free conditions into the iodine of 2.04 g (20 mmol) 1- hexanol, 0.38 g (5 mmol) of NH ₃ NHCO _2, and 2.54 g (10 mmol) in 20 mL vials, it is located in the pressure reactor And reacted at 100 DEG C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 6:

Was carried out in the same manner as in Example 26 in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The methanol in the solvent mixture, NH ₃ NHCO _2, And I < ₂ > were placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 27:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 2.5 mmol and 5 mmol, respectively, in the same manner as in Example 26. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 26 were obtained.

Example 28:

NH ₃ NHCO ₂ under non-solvent conditions I ₂ was reduced to 1.25 mmol and 2.5 mmol respectively, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 26 were obtained.

Example 29:

The reaction was carried out in the same manner as in Example 26 except that the reaction was carried out in an oven at 100 ° C for 12 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 26 were obtained.

Example 30:

The procedure of Example 26 was repeated except that the reaction was carried out in an oven at 100 ° C for 6 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 26 were obtained.

7. 1- Iodo -2- Methyl propane (One- iodo -2- 메틸opropane ) Synthesis of

Example 31:

Of the solvent under conditions 1.48 g (20 mmol) 2- methylpropan-1-ol, 0.38 g (5 mmol) of NH ₃ NHCO _2, And 2.54 g (10 mmol) of iodine were placed in a 20 mL vial, placed in a pressure reactor, and reacted at 100 DEG C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 7:

The reaction was carried out in the same manner as in Example 31, in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The methanol in the solvent mixture, NH ₃ NHCO _2, And I < ₂ > were placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 32:

Under solvent-free conditions NH ₃ NHCO ₂ And I ₂ were reduced to 2.5 mmol and 5 mmol, respectively, in the same manner as in Example 31. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 31 were obtained.

Example 33:

Under solvent-free conditions NH ₃ NHCO ₂ And I ₂ were respectively reduced to 1.25 mmol and 2.5 mmol, respectively. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 31 were obtained.

Example 34:

The reaction was carried out in the same manner as in Example 31, except that the reaction was conducted in an oven at 100 ° C for 12 hours under no-solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 31 were obtained.

Example 35:

The reaction was conducted in the same manner as in Example 31, except that the reaction was carried out in a 100 ° C oven under no solvent condition for 6 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 31 were obtained

8. 2- Iodopropane (2-Iodopropane) synthesis

Example 36:

Then under solvent-free conditions into the iodine of 1.20 g (20 mmol) isopropyl alcohol, 0.38 g (5 mmol) of NH ₃ NHCO _2, and 2.54 g (10 mmol) in 20 mL vial was placed in a pressure reactor, And reacted at 100 ° C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 8:

The reaction was carried out in the same manner as in Example 36, in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 37:

Except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 2.5 mmol and 5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 36 were obtained.

Example 38:

The procedure was as in Example 26 except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 1.25 mmol and 2.5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 36 were obtained.

Example 39:

The reaction was carried out in the same manner as in Example 26 except that the reaction was carried out in an oven at 100 ° C for 12 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 36 were obtained.

Example 40:

The procedure of Example 36 was repeated except that the reaction was carried out in an oven at 100 ° C for 6 hours under no solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 36 were obtained

9. Iodo Iodocyclohexane synthesis

Example 41:

Was placed under solvent-free conditions, the iodine of 2.00 g (20 mmol) cyclo-hexanol, 0.38 g (5 mmol) of NH ₃ NHCO _2, and 2.54 g (10 mmol) in 20 mL vial was placed in a pressure reactor, And reacted at 100 ° C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 9:

The reaction was carried out in the same manner as in Example 41, in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 42:

Except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 2.5 mmol and 5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 41 were obtained.

Example 43:

The procedure was as in Example 26 except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 1.25 mmol and 2.5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 41 were obtained.

Example 44:

The reaction was carried out in the same manner as in Example 41 except that the reaction was carried out in an oven at 100 ° C for 12 hours under no solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 41 were obtained.

Example 45:

The procedure of Example 41 was repeated, except that the reaction was conducted in an oven at 100 ° C for 6 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 41 were obtained

10. 3- Iodo -2,2- Dimethyl butane (3- iodo -2,2- dimethylbutane ) Synthesis of

Example 46:

Under solvent-free conditions NH ₃ of 4.24 g (20 mmol) 3,3- dimethyl mekil butane-2-ol, 0.38 g (5 mmol) NHCO 2, And 2.54 g (10 mmol) of iodine were placed in a 20 mL vial, placed in a pressure reactor, and reacted at 100 DEG C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 10:

Was carried out in the same manner as in Example 46 in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 47:

The procedure of Example 46 was repeated, except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 2.5 mmol and 5 mmol, respectively, under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 46 were obtained.

Example 48:

The procedure was as in Example 26 except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 1.25 mmol and 2.5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 46 were obtained.

Example 49:

The reaction was carried out in the same manner as in Example 46 except that the reaction was carried out in a 100 ° C oven under no solvent conditions for 12 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 46 were obtained.

Example 50:

The reaction was carried out in the same manner as in Example 46 except that the reaction was carried out in an oven at 100 ° C for 6 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the results were the same as those in Example 46

11. 2- Iodo -2- Methyl propane (2- iodo -2- 메틸opropane ) Synthesis of

Example 51:

Then under solvent-free conditions into the iodine of 1.40 g (20 mmol) 2- methyl-propan-2-ol, 0.38 g (5 mmol) of NH ₃ NHCO _2, and 2.54 g (10 mmol) in 20 mL vial, the pressure Placed in a reactor, and reacted at 100 DEG C for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and conversion and yield were respectively recorded over 98%.

Comparative Example 11:

The reaction was carried out in the same manner as in Example 51, in the presence of 10 mmol of HI (~ 55%) aqueous solution as a solvent. The mixture of methanol, NH ₃ NHCO ₂ , and I ₂ mixed in the solvent was placed in a pressure reactor and reacted in a 100 ° C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the conversion and yield were respectively 96% or more.

Example 52:

Except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 2.5 mmol and 5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 51 were obtained.

Example 53:

The procedure of Example 51 was repeated except that the amounts of NH ₃ NHCO ₂ and I ₂ were reduced to 1.25 mmol and 2.5 mmol respectively under solventless conditions. The mixture was placed in a pressure reactor and reacted in a 100 < 0 > C oven for 24 hours. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 51 were obtained.

Example 54:

The reaction was carried out in the same manner as in Example 51 except that the reaction was carried out in an oven at 100 ° C for 12 hours under no solvent conditions. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 51 were obtained.

Example 55:

The reaction was conducted in the same manner as in Example 51, except that the reaction was conducted in an oven at 100 ° C for 6 hours under no-solvent condition. The obtained product was analyzed by ¹ H and ¹³ C NMR, and the same results as in Example 51 were obtained

It was confirmed from the results of the above Examples and Comparative Examples that the alkyl halide can be obtained at a significantly higher conversion and yield, even when the solvent is not used, as confirmed in the above Examples. In addition, even though the conversion and yield are the same, in the case of the embodiments of the present invention, since the reaction is carried out under solvent-free conditions, the separation process for separating the product and the reactant in the entire process can be minimized There is an advantageous effect that the process can be performed.

The foregoing description of the disclosure is exemplary, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present invention .

Claims

A hydrazine derivative, an alcohol represented by ROH, and a halogen represented by X ₂ under non-solvent conditions to obtain a halogenated hydrocarbon represented by RX
/ RTI >
Wherein the hydrazine derivative is represented by the following formula (1)
Preparation of halogenated hydrocarbons:
[Chemical Formula 1]

In Formula 1,
R ₁ , R ₂ and R ₃ are each independently H; Or C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _3-20 cycloalkyl, C _3-20 cycloalkenyl group, a C _3-20 aliphatic hetero ring group, C _5-20 An aromatic hydrocarbon ring group, and a C _5-20 aromatic hydrocarbon ring group containing at least one hetero element,
In the ROH and RX, R is a linear or branched C _1-10 alkyl group or a C _3-10 cycloalkyl group,
Wherein X is F, Cl, Br, or I.

The method according to claim 1,
The C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _3-20 cycloalkyl, C _3-20 cycloalkenyl group, a C _3-20 aliphatic hetero ring group, C _5-20 The aromatic hydrocarbon ring group and the C _5-20 aromatic hydrocarbon ring group containing at least one hetero element are each composed of Si, O, S, Se, N, P, As, F, Cl, Br, &Lt; / RTI > wherein the at least one element comprises at least one element selected from the group consisting of:

The method according to claim 1,
Wherein the hydrazine derivative is a solid at room temperature.

delete

The method according to claim 1,
Wherein the yield of the halogenated hydrocarbon is 98% or more.

The method according to claim 1,
Wherein the reaction is carried out at a temperature of from 80 캜 to 200 캜.

The method according to claim 1,
Wherein the reaction is carried out under non-catalytic conditions.