JPH0532388B2 - - Google Patents
Info
- Publication number
- JPH0532388B2 JPH0532388B2 JP9700791A JP9700791A JPH0532388B2 JP H0532388 B2 JPH0532388 B2 JP H0532388B2 JP 9700791 A JP9700791 A JP 9700791A JP 9700791 A JP9700791 A JP 9700791A JP H0532388 B2 JPH0532388 B2 JP H0532388B2
- Authority
- JP
- Japan
- Prior art keywords
- diaminopropane
- item
- reaction
- pivalamide
- aminopropyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RWILRFIHGJCSIP-UHFFFAOYSA-N n-[3-(2,2-dimethylpropanoylamino)propyl]-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NCCCNC(=O)C(C)(C)C RWILRFIHGJCSIP-UHFFFAOYSA-N 0.000 claims description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 12
- GXZZIRGOAFXVBC-UHFFFAOYSA-N 6-amino-2,2-dimethylhexanamide Chemical compound NC(=O)C(C)(C)CCCCN GXZZIRGOAFXVBC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OTPDWCMLUKMQNO-UHFFFAOYSA-N 1,2,3,4-tetrahydropyrimidine Chemical compound C1NCC=CN1 OTPDWCMLUKMQNO-UHFFFAOYSA-N 0.000 description 3
- CYEGSNCGVMQQOP-UHFFFAOYSA-N 2-tert-butyl-1,2,3,4-tetrahydropyrimidine Chemical compound CC(C)(C)C1NCC=CN1 CYEGSNCGVMQQOP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- -1 ester azides Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 2
- BGNWXRJWDQHCRB-UHFFFAOYSA-N 2-propan-2-ylpyrimidine Chemical compound CC(C)C1=NC=CC=N1 BGNWXRJWDQHCRB-UHFFFAOYSA-N 0.000 description 2
- PXEJBTJCBLQUKS-UHFFFAOYSA-N 2-tert-butylpyrimidine Chemical compound CC(C)(C)C1=NC=CC=N1 PXEJBTJCBLQUKS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BUKMOQSSMTUSIG-UHFFFAOYSA-N 1-tert-butyl-5,6-dihydro-4h-pyrimidine Chemical compound CC(C)(C)N1CCCN=C1 BUKMOQSSMTUSIG-UHFFFAOYSA-N 0.000 description 1
- KZCLFWYVLDNEMU-UHFFFAOYSA-N 2-propan-2-yl-1,4,5,6-tetrahydropyrimidine Chemical compound CC(C)C1=NCCCN1 KZCLFWYVLDNEMU-UHFFFAOYSA-N 0.000 description 1
- DXHVLWFIWCJCLU-UHFFFAOYSA-N 3-tert-butyl-2,6-dihydro-1H-pyrimidine Chemical compound C(C)(C)(C)N1CNCC=C1 DXHVLWFIWCJCLU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005326 tetrahydropyrimidines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【0001】 テトラヒドロピリミジンの製造は「ピ
リミジン」インタサイエン（1962）、445頁ffに記
載されている。その好ましい反応は酢酸エチル又
は安息香酸エチルのような有機酸で１，３−ジア
ミノプロパン誘導体を還流することからなる。し
かしながらピバル酸ミチルがこの反応に使用され
た時、加水分解が起こり、そしてその得られた生
成物は錯体混合物であつた。[0001] The preparation of tetrahydropyrimidine is described in "Pyrimidine" Intasayen (1962), page 445 ff. The preferred reaction consists of refluxing the 1,3-diaminopropane derivative with an organic acid such as ethyl acetate or ethyl benzoate. However, when mityl pivalate was used in this reaction, hydrolysis occurred and the resulting product was a complex mixture.
【0002】 テトラヒドロピリミジン類そして特に
２−ｔ−ブチルテトラヒドロピリミジンは例外的
な殺虫作用を有するＯ−アルキル−Ｏ−〔ピリミ
ジン(5)イル〕−（チオノ）（チオール）−リン酸（ホ
スホン酸）エステル又はエステルアジトの製造用
の前駆物質として有利に使用される。これは米国
特許第4127652号に記載されている。Tetrahydropyrimidines and especially 2-tert-butyltetrahydropyrimidine are O-alkyl-O-[pyrimidin(5)yl]-(thiono)(thiol)-phosphonic acids with exceptional insecticidal activity. It is advantageously used as a precursor for the production of esters or ester azides. This is described in US Pat. No. 4,127,652.
【0003】 ３−アミノプロピルピバルアミドはピ
バル酸と１，３−ジアミノプロパンとをその１，
３−ジアミノプロパンの沸点以上の温度で接触さ
せることによつて高収率で製造できる。[0003] 3-Aminopropyl pivalamide is a combination of pivalic acid and 1,3-diaminopropane.
It can be produced in high yield by contacting at a temperature higher than the boiling point of 3-diaminopropane.
【0004】 蒸留による未反応の１，３−ジアミノ
プロパンを除去し、適当な溶剤でその反応混合物
を希釈し次いで還流によつて高収率で２−ｔ−ブ
チル−１，４，５，６−テトラヒドロピリミジン
を得る。[0004] Remove unreacted 1,3-diaminopropane by distillation, dilute the reaction mixture with a suitable solvent, and then reflux to obtain 2-t-butyl-1,4,5,6 in high yield. - obtain a tetrahydropyrimidine.
【0005】 この反応で作られた３−アミノプロピ
ルピバルアミドは新規は化合物であり副生物とし
てＮ，N′−１，３−プロパンジイルビス（２，
２−ジメチルプロパンアミド）が形成される。そ
の３−アミノプロピルピバルアミドは例外的な殺
虫作用を有する化合物製造用の中間体である２−
ｔ−ブチルテトラヒドロピリミジンを作るために
有利に使用される。[0005] 3-Aminopropyl pivalamide produced by this reaction is a new compound, and N,N'-1,3-propanediylbis(2,
2-dimethylpropanamide) is formed. Its 3-aminopropyl pivalamide is an intermediate for the production of compounds with exceptional insecticidal activity.
It is advantageously used for making t-butyltetrahydropyrimidine.
【0006】 その３−アミノプロピルピバルアミド
は、ピバル酸と過剰の１，３−ジアミノプロパン
とを110〜240℃、好ましくは200〜225℃で３〜12
時間反応させることによつて作られる。蒸留によ
る未反応の１，３−ジアミノプロパンの除去の
後、その残留物は適当な溶剤で稀釈されそしてそ
の得られた混合物は加圧又は加圧せずに110〜240
℃、好ましくは170〜190℃の温度で還流して２−
ｔ−ブチル−１，４，５，６−テトラヒドロピリ
ミジンを得る。[0006] The 3-aminopropyl pivalamide is produced by combining pivalic acid and excess 1,3-diaminopropane at 110 to 240°C, preferably 200 to 225°C for 3 to 12 hours.
Produced by a time reaction. After removal of unreacted 1,3-diaminopropane by distillation, the residue is diluted with a suitable solvent and the resulting mixture is heated at 110-240 °C with or without pressure.
℃, preferably 170-190℃ under reflux.
t-Butyl-1,4,5,6-tetrahydropyrimidine is obtained.
【0007】 適当な溶剤は、共沸混合物を形成する
不活性溶剤であり、それによつてその反応系から
水を除去するのに有用であり、そしてその溶剤は
大気圧条件で110〜240℃の沸点を有し又は適当な
圧力で110〜240℃で沸騰する他の不活性溶剤であ
つても良い。有利なことにその溶剤はトルエン、
Ｏ−キシレン又はジエチルベンゼンであり、もし
所望ならモノクロルベンゼン及びＯ−ジクロルベ
ンゼンのような塩素化ベンゼンも又使用できる。
大モル過剰の１，３−ジアミノプロパンが使用で
きるけれども３〜10モル過剰の１，３−ジアミノ
プロパンが通常使用される。もし３モル以下の過
剰の１，３−ジアミノプロパンが使用されるなら
ば収率は幾分低下する。[0007] Suitable solvents are inert solvents that form an azeotrope, thereby being useful for removing water from the reaction system, and that the solvent has a temperature of 110-240°C at atmospheric pressure conditions. Other inert solvents having a boiling point or boiling between 110 and 240°C at appropriate pressures may also be used. Advantageously, the solvent is toluene,
O-xylene or diethylbenzene and, if desired, chlorinated benzenes such as monochlorobenzene and O-dichlorobenzene can also be used.
A 3 to 10 molar excess of 1,3-diaminopropane is usually used, although large molar excesses of 1,3-diaminopropane can be used. If an excess of 1,3-diaminopropane of less than 3 moles is used, the yield decreases somewhat.
【0008】 ２−ｔ−ブチルピリミジンおよび他の
２−アルキルピリミジン類は水を発生させない条
件のもとで支持された貴金属触媒上に水を加えな
いで２−アルキルテトラヒドロピリミジンを脱水
素することからなる単一の工程反応で高収率でそ
して高純度で作られることが又発見された。[0008] 2-t-Butylpyrimidine and other 2-alkylpyrimidines are produced by dehydrogenating 2-alkyltetrahydropyrimidine without adding water over a supported noble metal catalyst under conditions that do not generate water. It has also been discovered that it can be made in high yield and with high purity in a single step reaction.
【0009】 例えばピリミジンのような不活性溶剤
が有利に使用されるけれども、この反応は溶剤を
使用せずに実施できる。[0009] Although inert solvents such as pyrimidine are advantageously used, the reaction can be carried out without the use of solvents.
【0010】 好ましい触媒はシリカゲル、木炭活性
炭、マグネシア又はアルミナ上に支持されている
白金又はパラジウムである。[0010] Preferred catalysts are platinum or palladium supported on silica gel, activated charcoal, magnesia or alumina.
【0011】 その反応温度250〜450℃、好ましくは
300〜400℃の範囲内である。溶剤を使用し又は使
用せずに所望のテトラヒドロピリミジンは所望の
温度にまで加熱されている支持された貴金属触媒
を含む充填カラムを通過させる。例えば触媒50ｇ
を含む１インチ×20インチ（2.5×51cm）カラム
のような蒸気気相反応器に対する供給速度は20〜
150ml／時間好ましくは40〜80ml／時間である。[0011] The reaction temperature is 250-450°C, preferably
It is within the range of 300-400℃. The desired tetrahydropyrimidine, with or without solvent, is passed through a packed column containing a supported noble metal catalyst that is heated to the desired temperature. For example, 50g of catalyst
Feed rates for vapor phase reactors such as 1 inch x 20 inch (2.5 x 51 cm) columns containing
150ml/hour, preferably 40-80ml/hour.
【0012】 水素の存在において水の発生を避ける
ために酸素はその反応帯域から除去されることが
必要である。酸素の除去は窒素又は二酸化炭素の
ような不活性ガスでその反応器を一掃させること
によつて有利に実施される。もし所望ならばその
不活性ガスはその触媒を活性化する役割を果たす
水素ガスを含んでいても良い。その場合脱水素反
応が進行するにつれて水素は存在するようにな
る。[0012] In order to avoid the evolution of water in the presence of hydrogen, it is necessary that oxygen be removed from the reaction zone. Oxygen removal is advantageously carried out by purging the reactor with an inert gas such as nitrogen or carbon dioxide. If desired, the inert gas may include hydrogen gas, which serves to activate the catalyst. In that case, hydrogen will be present as the dehydrogenation reaction progresses.
【0013】 本発明は下記の実施例により更に説明
される。[0013] The invention is further illustrated by the following examples.
【0014】
実施例 １
ピバル酸（136ｇ、1.33モル）と１，３−ジア
ミノプロパン（880ml、7.75モル）の混合物は撹
拌Parr反応器内で225℃で一昼夜加熱された。冷
却および蒸留による未反応１，３−ジアミノプロ
パンの除去の後、その残留物のガスクロマトグラ
フ分析により蒸留により精製に安定でない粘ちよ
うな油状物質は90％収率の３−アミノプロピルピ
バルアミドであつた。Example 1 A mixture of pivalic acid (136 g, 1.33 mol) and 1,3-diaminopropane (880 ml, 7.75 mol) was heated at 225° C. overnight in a stirred Parr reactor. After cooling and removal of unreacted 1,3-diaminopropane by distillation, gas chromatographic analysis of the residue revealed a viscous oil that was not stable to purification by distillation and yielded 3-aminopropylpivalamide in 90% yield. It was hot.
【0015】 その残留物をＯ−キシレン（250ml）
で稀釈しそしてその混合物をデイアン（Dean）
およびスターク（Stark）装置内で48時間還流し
て循環脱水を行つた。共沸混合物を分離した後、
Ｏ−キシレンを蒸発させ133〜135℃の融点を持つ
２−ｔ−ブチルテトラヒドロピリミジン167ｇ
（90％収率）を得た。[0015] The residue is O-xylene (250ml)
dilute the mixture with Dean
The mixture was then refluxed for 48 hours in a Stark apparatus for cyclic dehydration. After separating the azeotrope,
167 g of 2-t-butyltetrahydropyrimidine with a melting point of 133-135°C by evaporation of O-xylene
(90% yield) was obtained.
【0016】
実施例 ２
トリメチル酢酸25.5ｇ（0.25モル）と１，３−
ジアミノプロパン100ml（112.6ｇ、1.52モル）の
混合物を200〜210℃で16時間加熱した。冷却およ
び過剰の１，３−ジアミノプロパンの除去の後、
その残留物、３−アミノプロピルピバルアミド、
粘ちような油状物質はNMRによつて分析されそ
して３−アミノプロピルピバルアミドと一致する
スペクトルを与えた。Example 2 25.5g (0.25mol) of trimethylacetic acid and 1,3-
A mixture of 100 ml (112.6 g, 1.52 mol) of diaminopropane was heated at 200-210°C for 16 hours. After cooling and removal of excess 1,3-diaminopropane,
The residue, 3-aminopropyl pivalamide,
The sticky oil was analyzed by NMR and gave a spectrum consistent with 3-aminopropyl pivalamide.
【0017】 上記残留物の半分を室温でトリエチル
アミンおよびトリメチルアセチルクロライドの
各々等量と反応させた。[0017] Half of the above residue was reacted with equal amounts each of triethylamine and trimethylacetyl chloride at room temperature.
【0018】 その生成物をミチレンクロライドによ
り抽出により分離し、氷で三回洗浄し、MgSO4
上で乾燥し、その溶剤を蒸発させそしてその生成
物を冷却して結晶化した。その濾過および乾燥し
た生成物Ｎ，N′−１，３−プロパノンジイルビ
ス（２，２−ジメチプロパンアミド）（18.5ｇ）
は120〜122℃の融点を有し、93.6％の収率であつ
た。そのNMRスペクトルは１，３−ジアミノプ
ロパンとトリメチルアセチルクロライドから直接
作られたサンプルのNMRスペクトルと同等であ
つた。[0018] The product was isolated by extraction with methylene chloride, washed three times with ice, and extracted with MgSO 4
The solvent was evaporated and the product crystallized on cooling. The filtered and dried product N,N'-1,3-propanonediylbis(2,2-dimethypropanamide) (18.5g)
had a melting point of 120-122°C and a yield of 93.6%. The NMR spectrum was comparable to that of a sample made directly from 1,3-diaminopropane and trimethylacetyl chloride.
【0019】
分 析
Ｃ Ｈ Ｎ
理論値（C13H26N2O2） 64.46 10.74 11.57
分析値 64.50 11.02 11.60
実施例 ３
ピリジン100ml中の２−イソプロピル−１，４，
５，６−テトラヒドロピリミジン70ｇの溶液をア
ルミナ上に0.5％プラチナ約50ｇを含む１インチ
×20インチカラムに300〜325℃で窒素および水素
の混合物をそのカラムに流しながら、約１ml／分
で供給した。その触媒は２時間その触媒床上に
H2／N22：１の流れを流すことによつて活性化
した。その流出物は蒸留され152〜155℃の沸点の
２−イソプロピルピリミジンを与えた。その収率
は73％であつた。Analysis C H N Theoretical value (C 13 H 26 N 2 O 2 ) 64.46 10.74 11.57 Analytical value 64.50 11.02 11.60 Example 3 2-isopropyl-1,4, in 100 ml of pyridine
A solution of 70 g of 5,6-tetrahydropyrimidine is fed to a 1 inch x 20 inch column containing about 50 g of 0.5% platinum on alumina at about 1 ml/min at 300-325°C with a mixture of nitrogen and hydrogen flowing through the column. did. The catalyst was left on the catalyst bed for 2 hours.
Activation was achieved by flowing a 2:1 flow of H 2 /N 2 . The effluent was distilled to give 2-isopropylpyrimidine with a boiling point of 152-155°C. The yield was 73%.
【0020】 上記の操作は２−ｔ−ブチル−１，
４，５，６−テトラヒドロピリミジンの量を変え
溶剤の量を変え、アルミナ上に0.5％パラジウム
および250〜420℃の温度を使用して繰り返した。
２−ｔ−ブチルピリミジンの収率は58〜86％であ
つた。[0020] The above operation is performed using 2-t-butyl-1,
It was repeated using varying amounts of 4,5,6-tetrahydropyrimidine and varying amounts of solvent, 0.5% palladium on alumina, and temperatures from 250 to 420°C.
The yield of 2-t-butylpyrimidine was 58-86%.
【0021】 同様の結果は例えばキノリンのような
他の溶剤を使用して得られた。[0021] Similar results were obtained using other solvents such as quinoline.
【0022】
実施例 ４
２−イソプロピル−１，４，５，６−テトラヒ
ドロピリミジン91.6ｇを蒸気相脱水素器（１イン
チ×20インチ）にN2およびH2の流れを流しなが
らアルミナ上に0.5％パラジウム50ｇを含むその
脱水素器に滴下しながら供給した。その反応器温
度は310℃であつた。その生成物は155℃の沸点を
有する２−イソプロピルピリミジン67ｇ（収率86
％）を得た。Example 4 91.6 g of 2-isopropyl-1,4,5,6-tetrahydropyrimidine was deposited on alumina in a vapor phase dehydrogenator (1 inch x 20 inches) with a flow of N2 and H2 . % palladium was added dropwise to the dehydrogenator. The reactor temperature was 310°C. The product was 67 g of 2-isopropylpyrimidine with a boiling point of 155°C (yield 86
%) was obtained.
【0023】 本発明の実施態様 第１項 ３−アミノプロピルピバルアミド。[0023] Embodiments of the invention Item 1 3-Aminopropyl pivalamide.
【0024】第２項
Ｎ，N′−１，３−プロパジイルビス（２，２
−ジメチルプロパンアミド）。[0024] Second term N,N'-1,3-propadiylbis(2,2
-dimethylpropanamide).
【0025】第３項
ピバル酸と１，３−ジアミノプロパンとをその
１，３−ジアミノプロパンの沸点以上の温度で触
媒の不存在において接触させ、そして蒸留により
過剰の１，３−ジアミノプロパンを除去すること
を含む３−アミノプロピルピバルアミドを製造す
る方法。Item 3: Contact pivalic acid and 1,3-diaminopropane in the absence of a catalyst at a temperature above the boiling point of the 1,3-diaminopropane, and remove excess 1,3-diaminopropane by distillation. A method of producing 3-aminopropyl pivalamide, comprising removing 3-aminopropyl pivalamide.
【0026】第４項
その反応は110〜240℃で実施される上記第３項
記載の方法。Item 4: The method according to item 3 above, wherein the reaction is carried out at 110-240°C.
【0027】第５項
その反応が200〜225℃で実施される上記第３項
記載の方法。Item 5: The method according to item 3 above, wherein the reaction is carried out at 200-225°C.
【0028】第６項
その１，３−ジアミノプロパンは化学量論量よ
り３〜10モル過剰に存在する上記第３項記載の方
法。Item 6: The method according to item 3 above, wherein the 1,3-diaminopropane is present in a 3 to 10 molar excess over the stoichiometric amount.
【0029】第７項
酸素の不存在においてそして支持された触媒上
に水を加えることなしに蒸気相反応器内で２−ア
ルキルテトラヒドロピリミジンを脱水素すること
からなる２−アルキルピリミジンを製造する方
法。Section 7. Process for producing 2-alkylpyrimidines comprising dehydrogenating 2-alkyltetrahydropyrimidine in a vapor phase reactor in the absence of oxygen and without adding water onto a supported catalyst. .
【0030】第８項
２−アルキルテトラヒドロピリミジンは２‐イ
ソプロピルテトラヒドロピリミジン又は２−第三
級−ブチルテトラヒドロピリミジンである上記第
７項記載の方法。Item 8 The method according to Item 7, wherein the 2-alkyltetrahydropyrimidine is 2-isopropyltetrahydropyrimidine or 2-tertiary-butyltetrahydropyrimidine.
【0031】第９項
その反応は250〜450℃で行われる上記第８項記
載の方法。Item 9 The method according to item 8 above, wherein the reaction is carried out at 250 to 450°C.
【0032】第10項
その触媒はアルミナ上に支持された白金又はパ
ラジウムである上記第９項記載の方法。Item 10. The method of item 9 above, wherein the catalyst is platinum or palladium supported on alumina.
Claims (1)
ルビス（２，２−ジメチルプロパンアミド）。Claim 1: N,N'-1,3-propanediylbis(2,2-dimethylpropanamide).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9700791A JPH04234836A (en) | 1991-04-26 | 1991-04-26 | N,n'-1,3-propanediylbis(2,2-dimethylpropanamide) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9700791A JPH04234836A (en) | 1991-04-26 | 1991-04-26 | N,n'-1,3-propanediylbis(2,2-dimethylpropanamide) |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58035709A Division JPS59164757A (en) | 1981-09-14 | 1983-03-04 | Novel aminopropylpivalamides, manufacture and use for producing 2-tertiary-butyl-1,4,5,6-tetrahydropyrimidine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04234836A JPH04234836A (en) | 1992-08-24 |
| JPH0532388B2 true JPH0532388B2 (en) | 1993-05-14 |
Family
ID=14180205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9700791A Granted JPH04234836A (en) | 1991-04-26 | 1991-04-26 | N,n'-1,3-propanediylbis(2,2-dimethylpropanamide) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04234836A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482884B1 (en) | 2000-02-28 | 2002-11-19 | Pirelli Pneumatici S.P.A. | Silica reinforced rubber compositions of improved processability and storage stability |
-
1991
- 1991-04-26 JP JP9700791A patent/JPH04234836A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04234836A (en) | 1992-08-24 |
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