Method of producing alkylated diamines

专利摘要:
A process for alkylating a polyamine by contacting, in a liquid media, a polyamine, an olefinic compound, carbon monoxide, and a hydrogen source in the presence of a catalytic amount of a rhodium atom containing compound selected from metallic rhodium, rhodium salts, rhodium oxides, rhodium carbonyls and ligands thereof at a temperature of from about 50 DEG C. to 250 DEG C. and at a pressure of from about 30 to about 300 atmospheres.
公开号:SU1308194A3
申请号:SU813260000
申请日:1981-02-20
公开日:1987-04-30
发明作者:Ячимович Фелек
申请人:В.Р.Грейс Энд Ко.(Фирма)；
IPC主号:

专利说明:

The invention relates to an improved process for the preparation of alkylated diamines, which are widely used as surfactants, flocculating agents, softeners, and also as a component in some coating compositions.
The purpose of the invention is to simplify the process.
Example 1. 10.8 g of piperazine, 25.3 ml of cyclohexene, 0.9 ml of water (0.05 mol of HjO), 25 ml of N-methylpiperidine are placed in a 150 ml stainless steel vessel. 370 mg industrially1 tris (dimethylphenylphosphine) -hexafluorophosphine-rhodium-norbornadiene RhCNBD) (CHj) () PF is placed in the reactor. The reactor is sealed and pumped with carbon monoxide to a pressure of 68 atm. The molar ratio is 8.3: 1. The reactor is placed in an oil bath of a bitch for 6 hours at 140 ° C, then cooled to ambient temperature. The contents are removed from the reactor and washed with diethyl ether and water. The ether extracts are collected and evaporated to dryness. The solid product is recrystallized. from methanol. The resulting 1,4-bis (cyclohexylmethyl) piperazine (yield 70%) was identified by proton NMR.
EXAMPLE 2: Example 1 is repeated.
fO
t5
tori are taken in such an amount that the molar ratio of olefin to rhodium atoms is 500. The reactor is sealed, pumped with carbon monoxide (0.83 mol) to a pressure of 68 atm at a molar ratio of 2: 1, placed in an oil bath-tr bitch on 7 h at, then cooled to room temperature. The contents are recovered and the separated product is analyzed by gas-liquid chromatography. Each experiment gave the following percent conversion to tertiary amine,%:
Rhfc (CO) 95
RhCl3 (C5HjN) 3 92 Rh (CO) 2 (C rH702) 94
RhCKC Hg i9
Example 4: Example 3 is repeated.
but instead of N-methylpiperidine, ethanol is used as the solvent, and RhCl () is used as the catalyst. As in Example 3, the molar ratio CO / H20 is 8: 1. The isolated product was analyzed by gas-liquid chromatography and identified as a tertiary amine, the yield of which is 94%.
EXAMPLE 5 Example 3 is repeated, but instead of piperazine, industrial phenylenediamine, N, N-diphenylethylenediamine and hexamethylenediamine, each of which is equivalent to piperazine, are used as a reagent.
20
thirty
using 134 ml of cyclohexene, g 3 quantities. In each case, a mole of p-50 gpiperazine, 42 ml of water (0.23 mol), the CO / IGO ratio was 8: 1.
The product obtained in each case, analyze the standard method. 06200 ml of N-methylpiperidine and 400 mg of the same rhodium catalyst. The reagents are placed in a 2-liter stainless steel reactor, which is sealed and pumped at ambient temperature with carbon monoxide (5.56 mol CO) to a pressure of 68 atm at a molar ratio of 24: 1. The reaction is carried out at 150 ° C for 8 hours. The isolated tertiary diamine is identified by proton NMR (70% yield).
PRI me R 3. Conducted experiments using various rhodium catalysts. In each experience 1.06 x
ten
-2
ten
-3
-2
MOL of cyclohexene, 5.3 x mol of piperazine, 1.06 x X 10 mol of water are placed in a stainless steel reactor with a volume of 30 ml containing 2 ml of N-methylpiperidine and the selected rhodium catalyst, which is listed below. Each ns is catalyzed that the transformations are similar to 40 as those obtained in Example 3. Respectively obtained 1,4-bis (cyclohexylmethyl) -aminobenzene, 1,2-bis bis (M-phenyl-N-cyclohexylmethyl) amy , HoJ-ethane, 1,6-bis- (cyclohexylmethyl). Amino-hexane.
EXAMPLE 6 The procedure described in Example 3 is repeated, except that the piperazine reagent is replaced with an equivalent amount of industrial H, H -dimethylstilenediamine (the molar ratio is 8: 1). The isolated tertiary amine is analyzed in each trial by the traditional method - gas-liquid chromatography. The tertiary amine transformations were found to be similar to those obtained. in example 3.
 50
five
tori are taken in such an amount that the molar ratio of olefin to rhodium atoms is 500. The reactor is sealed, pumped with carbon monoxide (0.83 mol) to a pressure of 68 atm at a molar ratio of 2: 1, placed in an oil bath-tr bitch on 7 h at, then cooled to room temperature. The contents are recovered and the separated product is analyzed by gas-liquid chromatography. Each experiment gave the following percent conversion to tertiary amine,%:
Rhfc (CO) 95
RhCl3 (C5HjN) 3 92 Rh (CO) 2 (C rH702) 94
RhCKC Hg i9
Example 4: Example 3 is repeated.
but instead of N-methylpiperidine, ethanol is used as the solvent, and RhCl () is used as the catalyst. As in Example 3, the molar ratio CO / H20 is 8: 1. The isolated product was analyzed by gas-liquid chromatography and identified as a tertiary amine, the yield of which is 94%.
EXAMPLE 5 Example 3 is repeated, but instead of piperazine, industrial phenylenediamine, N, N-diphenylethylenediamine and hexamethylenediamine, each of which is equivalent to piperazine, are used as a reagent.
0
0
It was found that the transformations are similar to 40 as those obtained in Example 3. 1,4-bis (cyclohexylmethyl) -aminobenzene, 1,2-β-bis C (M-phenyl-N-cyclohexylmethyl) ami, respectively, were obtained respectively. , HoJ-ethane, 1,6-bis- (cyclohexylmethyl). Amino-hexane.
EXAMPLE 6 The procedure described in Example 3 is repeated, except that the piperazine reagent is replaced with an equivalent amount of industrial H, H -dimethylstilenediamine (the molar ratio is 8: 1). The isolated tertiary amine is analyzed in each trial by the traditional method - gas-liquid chromatography. The tertiary amine transformations were found to be similar to those obtained. in example 3.
50
313
Example. The procedure described in Example 3 is repeated, except that cyclohexene is replaced with equivalent molar amounts of commercially available double bond compounds: hexene-1, butene-1, propenome-1 and octene-1 (molar ratio CO / H20 8: 1). The obtained tertiary amine in each working cycle is analyzed in the traditional way (GLC). It was found that the product yield is as high as in example 3.
EXAMPLE 8 The procedure described in Example 3 is repeated, except that the pressure while supplying carbon monoxide (0.129 mol CO, molar ratio 12: 1) is increased to 102 atm and again repeated. pumping carbon monoxide (0.04 mol) under a pressure of 34 atm (molar ratio C0 / H20 4: 1). In each working cycle, a tertiary amine is obtained, which is analyzed by a conventional method. In cycles using loading at a pressure of 102 atm, a high product yield was obtained, which is similar to the example, and at a pressure of 30 atm, a lower product yield. Example9. The procedure described in Example 3 is repeated, except for the addition of the catalysts that additionally use rhodium dioxide and the reactions are repeated at 100–200 ° C. The molar ratio of C0 / H2 is 0 8: 1. In each working cycle, the resulting tertiary amine is analyzed by gas-liquid chromatography.
The proposed method for the alkylation of diamines is simpler than the known method alky
Editor M.Petrova Order 1645/58
Compiled by L.Ioffe Tehred M.Hodanich
Proofreader M.Sha
Circulation 372Subscribe
VNIIPI USSR State Committee for Inventions and Discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
Production and printing company, Uzhgorod, Projecto st., 4
JO
81
five
944
liaing dia :: ins with aldehyde, since it is one-step (the known method requires two stages and a more expensive starting product).

权利要求:
Claims (1)
[1]
Invention Formula
The method of producing alkyl diamines by alkylation of amines of the formula
N - R .. - N
Uh
R.
H
where R and R each is hydrogen, phenyl
or C-C-alkyl
or R and Rj together - C2-alkylene
a nitrogen bonding group;
R, - C —C-alkylene radical,
in an inert organic solvent, characterized in that, in order to simplify the process, the alkylation is carried out with a C-Cd-olefin in the presence of carbon monoxide supplied at a pressure of 30-100 atm and water, and the molar ratio of olefin to amine is em 1-2: 1, water to amine - 2-5: 1 and carbon monoxide to water - 24-3: 1, and the process is carried out at 100-200 0 in the presence of a catalytic amount of one of the following catalysts Rh (NBD ) (CH3) jP (CbH5), PF6, Rht (CO), RhCl3 (Cj; HyN) 3, Rh (CO) 2 (CgH /) 2), RhCl (C, Hg) 2j, RhO.
Proofreader M.Sharopsh

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同族专利:

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公开号 | 公开日

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DE3105895A1|1981-11-19|

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IT8026422D0|1980-12-03|

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ES499653A0|1982-02-01|

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SE453495B|1988-02-08|

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SE8009107L|1981-08-23|

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GB2070011A|1981-09-03|

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IT1141107B|1986-10-01|

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FI68805B|1985-07-31|

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ES8202842A1|1982-02-01|

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FR2476642A1|1981-08-28|

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US4322530A|1982-03-30|

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GB2070011B|1984-04-04|

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FI68805C|1985-11-11|

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NL8006673A|1981-09-16|

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FR2476642B1|1985-07-05|

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BE887630A|1981-06-15|

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FI804065L|1981-08-23|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US06/123,823|US4322530A|1980-02-22|1980-02-22|Alkylation of polyamines|

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