JP2010215590A - Method of producing compound comprising ureido group - Google Patents
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- JP2010215590A JP2010215590A JP2009066131A JP2009066131A JP2010215590A JP 2010215590 A JP2010215590 A JP 2010215590A JP 2009066131 A JP2009066131 A JP 2009066131A JP 2009066131 A JP2009066131 A JP 2009066131A JP 2010215590 A JP2010215590 A JP 2010215590A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- -1 aromatic hydroxy compound Chemical class 0.000 claims description 7
- 150000002825 nitriles Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- NSENZNPLAVRFMJ-UHFFFAOYSA-N 2,3-dibutylphenol Chemical compound CCCCC1=CC=CC(O)=C1CCCC NSENZNPLAVRFMJ-UHFFFAOYSA-N 0.000 description 1
- RLEWTHFVGOXXTN-UHFFFAOYSA-N 2,3-diethylphenol Chemical compound CCC1=CC=CC(O)=C1CC RLEWTHFVGOXXTN-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- IXKVYSRDIVLASR-UHFFFAOYSA-N 2,3-dioctylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1CCCCCCCC IXKVYSRDIVLASR-UHFFFAOYSA-N 0.000 description 1
- HRQPPTDGMMGDKC-UHFFFAOYSA-N 2,3-dipropylphenol Chemical compound CCCC1=CC=CC(O)=C1CCC HRQPPTDGMMGDKC-UHFFFAOYSA-N 0.000 description 1
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OJLHBQIGOFOFJF-UHFFFAOYSA-N 6-(carbamoylamino)hexylurea Chemical compound NC(=O)NCCCCCCNC(N)=O OJLHBQIGOFOFJF-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SCTYZODHGNFGEI-UHFFFAOYSA-N NC(=O)N.NC(=O)N.C1(CCCCC1)CC1CCCCC1 Chemical compound NC(=O)N.NC(=O)N.C1(CCCCC1)CC1CCCCC1 SCTYZODHGNFGEI-UHFFFAOYSA-N 0.000 description 1
- QKUWWVKSHZZXRX-UHFFFAOYSA-N NC(N)=O.NC(N)=O.CC1=CC(=O)CC(C)(C)C1 Chemical compound NC(N)=O.NC(N)=O.CC1=CC(=O)CC(C)(C)C1 QKUWWVKSHZZXRX-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DNKLMUSYHDECGI-UHFFFAOYSA-N benzylbenzene urea Chemical compound NC(=O)N.NC(=O)N.C1(=CC=CC=C1)CC1=CC=CC=C1 DNKLMUSYHDECGI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- OXILGXRAFYNZTD-UHFFFAOYSA-N naphthalene urea Chemical compound NC(=O)N.NC(=O)N.C1=CC=CC2=CC=CC=C12 OXILGXRAFYNZTD-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、ウレイド基を有する化合物の製造方法に関する。 The present invention relates to a method for producing a compound having a ureido group.
ウレイド基を有する化合物は、医薬品、農薬等の原料として、工業的に有用な化合物であり、これまで、ウレイド基を有する様々な化合物が提示されている（例えば、特許文献１、特許文献２）。 A compound having a ureido group is an industrially useful compound as a raw material for pharmaceuticals, agricultural chemicals and the like, and various compounds having a ureido group have been proposed so far (for example, Patent Document 1 and Patent Document 2). .
ウレイド基を有する化合物の製造方法としては、例えば、非特許文献１には、溶融状態の大過剰の尿素にアミン化合物を添加し、１，６−ヘキサンジウレアを製造する方法が開示されている。 As a method for producing a compound having a ureido group, for example, Non-Patent Document 1 discloses a method for producing 1,6-hexanediurea by adding an amine compound to a large excess of urea in a molten state.
しかしながら、当該方法では、生成したウレイド基を有する化合物の末端の尿素結合が更に尿素と反応するため、末端にビウレット結合を有する化合物が副生し、収率が低下する場合が多かった。 However, in this method, since the urea bond at the end of the compound having a ureido group is further reacted with urea, a compound having a biuret bond at the end is often produced as a by-product, resulting in a decrease in yield.
本発明の目的は、ウレイド基を有する化合物を簡便に収率よく製造する方法を提供することにある。 An object of the present invention is to provide a method for easily producing a compound having a ureido group with a high yield.
そこで、本発明者らは、上記課題に対し鋭意検討を重ねた結果、特定の条件下において、イソシアネートとアンモニアとを反応させることによりウレイド基を有する化合物を簡便に収率よく製造できることを見出し、本発明を完成させるに至った。 Therefore, as a result of intensive studies on the above problems, the present inventors have found that a compound having a ureido group can be easily produced in a high yield by reacting isocyanate and ammonia under specific conditions. The present invention has been completed.
すなわち、本発明は、
［１］イソシアネートとアンモニアとの反応による、ウレイド基を有する化合物の製造方法であって、前記反応が溶媒中で行われ、前記溶媒に含有される水の量が０．０１ｐｐｍ〜２０ｐｐｍ、前記アンモニアに含有される水の量が０．００１ｐｐｍ〜１０ｐｐｍである製造方法、
That is, the present invention
[1] A method for producing a compound having a ureido group by reaction of isocyanate and ammonia, wherein the reaction is performed in a solvent, and the amount of water contained in the solvent is 0.01 ppm to 20 ppm, and the ammonia A production method wherein the amount of water contained in the water is 0.001 ppm to 10 ppm,
［２］前記イソシアネートは、下記一般式（１）で表される化合物である［１］記載の製造方法、
［式中、Ｒ１は、炭素数１〜２０のｎ価の脂肪族基又は炭素数６〜２０のｎ価の芳香族基を示し、ｎは、２〜１０の整数を示す。］
[2] The production method according to [1], wherein the isocyanate is a compound represented by the following general formula (1):
[Wherein, R 1 represents an n-valent aliphatic group having 1 to 20 carbon atoms or an n-valent aromatic group having 6 to 20 carbon atoms, and n represents an integer of 2 to 10]. ]
［３］前記ウレイド基を有する化合物は、下記一般式（２）で表される化合物である［１］又は［２］記載の製造方法、
［式中、Ｒ１は、炭素数１〜２０のｎ価の脂肪族基又は炭素数６〜２０のｎ価の芳香族基を示し、ｎは、２〜１０の整数を示す。］
[3] The production method according to [1] or [2], wherein the compound having a ureido group is a compound represented by the following general formula (2):
[Wherein, R 1 represents an n-valent aliphatic group having 1 to 20 carbon atoms or an n-valent aromatic group having 6 to 20 carbon atoms, and n represents an integer of 2 to 10]. ]
［４］前記溶媒は、窒素、酸素及び硫黄からなる群より選ばれる原子を、少なくとも１つ含有する化合物である［１］〜［３］のいずれかに記載の製造方法、 [4] The production method according to any one of [1] to [3], wherein the solvent is a compound containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur.
［５］前記溶媒は、ニトリルである［１］〜［４］のいずれかに記載の製造方法、 [5] The production method according to any one of [1] to [4], wherein the solvent is nitrile.
［６］前記溶媒は、芳香族ヒドロキシ化合物である［１］〜［４］のいずれかに記載の製造方法、
を提供する。
[6] The production method according to any one of [1] to [4], wherein the solvent is an aromatic hydroxy compound,
I will provide a.
本発明の製造方法により、簡便に収率よくウレイド基を有する化合物を製造することができる。 By the production method of the present invention, a compound having a ureido group can be easily produced with a high yield.
以下、本発明を実施するための形態（以下、「本実施の形態」という。）について詳細に説明する。なお、本発明は以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
先ず、本実施形態で使用されるイソシアネートを説明する。本実施形態で使用されるイソシアネートは、下記一般式（１）で表される化合物である。なお、Ｒ１は、炭素数１〜２０のｎ価の脂肪族基又は炭素数６〜２０のｎ価の芳香族基を示し、ｎは、２〜１０の整数を示す。
上記式（１）として使用される化合物としては、ｎが２以上のポリイソシアネートが好ましく、ｎが２であるジイソシアネートがより好ましい。 As a compound used as said Formula (1), n is a polyisocyanate with 2 or more, and the diisocyanate whose n is 2 is more preferable.
このようなポリイソシアネートとしては、Ｒ１が炭素数１〜２０の脂肪族基（鎖状でも環状でもよい。）又は炭素数６〜２０の芳香族基である化合物を使用する。例えば、ヘキサメチレンジイソシアネート、トリレンジイソシアネート（各異性体）、ジフェニルメタンジイソシアネート（各異性体）、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート（各異性体）、ナフタレンジイソシアネート（各異性体）、テトラメチレンキシリレンジイソシアネート（各異性体）、トリメチルヘキサメチレンジイソシアネート（各異性体）、キシリレンジイソシアネート（各異性体）、水添キシリレンジイソシアネート（各異性体）、又はノルボルネンジイソシアネート等を挙げることができる。また、上記脂肪族基及び芳香族基は、酸素原子を有していてもよい。 As such a polyisocyanate, a compound in which R 1 is an aliphatic group having 1 to 20 carbon atoms (which may be linear or cyclic) or an aromatic group having 6 to 20 carbon atoms is used. For example, hexamethylene diisocyanate, tolylene diisocyanate (each isomer), diphenylmethane diisocyanate (each isomer), isophorone diisocyanate, dicyclohexylmethane diisocyanate (each isomer), naphthalene diisocyanate (each isomer), tetramethylene xylylene diisocyanate (each Isomers), trimethylhexamethylene diisocyanate (each isomer), xylylene diisocyanate (each isomer), hydrogenated xylylene diisocyanate (each isomer), norbornene diisocyanate, and the like. Moreover, the said aliphatic group and aromatic group may have an oxygen atom.
次に、イソシアネートとアンモニアとを反応させてウレイド基を有する化合物を製造する方法について説明する。 Next, a method for producing a compound having a ureido group by reacting isocyanate and ammonia will be described.
反応は溶媒中で行われる。溶媒としては、窒素、酸素、及び硫黄からなる群から選ばれる原子を少なくとも１つ有する化合物が好ましく使用される。例えば、ニトリル、ヒドロキシ化合物、エーテル、チオール等を挙げることができるが、中でも、ニトリル、芳香族ヒドロキシ化合物が好ましく使用される。これらの好ましい化合物としては、アセトニトリル、フェノール、種々の置換フェノールを挙げることができる。更に置換フェノールとしては、例えば、メチルフェノール、エチルフェノール、プロピルフェノール（各異性体）、ブチルフェノール（各異性体）、ペンチルフェノール（各異性体）、オクチルフェノール（各異性体）、ノニルフェノール（各異性体）、デシルフェノール（各異性体）、ドデシルフェノール（各異性体）等のモノ置換フェノール、ジメチルフェノール（各異性体）、ジエチルフェノール（各異性体）、ジプロピルフェノール（各異性体）、ジブチルフェノール（各異性体）、ジペンチルフェノール（各異性体）、ジオクチルフェノール（各異性体）、ジノニルフェノール（各異性体）、ジデシルフェノール（各異性体）等のジ置換フェノール等を挙げることができる。 The reaction is carried out in a solvent. As the solvent, a compound having at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur is preferably used. For example, nitriles, hydroxy compounds, ethers, thiols and the like can be mentioned. Among them, nitriles and aromatic hydroxy compounds are preferably used. Examples of these preferable compounds include acetonitrile, phenol, and various substituted phenols. Furthermore, as substituted phenol, for example, methylphenol, ethylphenol, propylphenol (each isomer), butylphenol (each isomer), pentylphenol (each isomer), octylphenol (each isomer), nonylphenol (each isomer) , Monosubstituted phenols such as decylphenol (each isomer), dodecylphenol (each isomer), dimethylphenol (each isomer), diethylphenol (each isomer), dipropylphenol (each isomer), dibutylphenol ( Each isomer), dipentylphenol (each isomer), dioctylphenol (each isomer), dinonylphenol (each isomer), didecylphenol (each isomer) and the like can be mentioned.
上記の溶媒の使用量は、イソシアネートに対して、化学量論比で、好ましくは１倍〜１００００倍の範囲と、より好ましくは５倍〜５０００倍の範囲と、更に好ましくは１０倍〜１０００倍の範囲とする。 The amount of the solvent used is stoichiometric with respect to the isocyanate, preferably in the range of 1 to 10000 times, more preferably in the range of 5 to 5000 times, and even more preferably in the range of 10 to 1000 times. The range.
一般的に、イソシアネートは水により容易に分解されることが知られている（例えば、「化学大辞典１」、共立出版社、２００３年、６０７頁参照）ことから、反応系中に含有される水の量は少ない方がよいとされる。しかしながら、本発明者らは、反応系中に含有される少量の水によって、イソシアネートとアンモニアとの反応が促進される場合があることを見出した。このような効果を奏する機構は明確ではないが、少量の水がアンモニアの溶媒への溶解を助け、溶媒中のアンモニア濃度が高まるためではないかと推測される。 In general, it is known that isocyanate is easily decomposed by water (see, for example, “Chemical Dictionary 1”, Kyoritsu Publishing Co., Ltd., 2003, page 607), and is therefore contained in the reaction system. The amount of water should be small. However, the present inventors have found that the reaction between isocyanate and ammonia may be promoted by a small amount of water contained in the reaction system. Although the mechanism that exerts such an effect is not clear, it is presumed that a small amount of water helps dissolution of ammonia in the solvent and the concentration of ammonia in the solvent increases.
以上のような観点から、溶媒に含有される水の量は、０．０１ｐｐｍ〜２０ｐｐｍ、好ましくは０．０３ｐｐｍ〜１０ｐｐｍ、より好ましくは０．０５ｐｐｍ〜１０ｐｐｍである。 From the above viewpoints, the amount of water contained in the solvent is 0.01 ppm to 20 ppm, preferably 0.03 ppm to 10 ppm, more preferably 0.05 ppm to 10 ppm.
また、同様の観点から、アンモニアに含有される水の量は、０．００１ｐｐｍ〜１０ｐｐｍ、好ましくは０．００５ｐｐｍ〜５ｐｐｍである。 From the same viewpoint, the amount of water contained in ammonia is 0.001 ppm to 10 ppm, preferably 0.005 ppm to 5 ppm.
反応温度は、２０℃〜３００℃の範囲とする。反応速度を高めるためには高温が好ましいが、一方で、高温では好ましくない反応も起こる場合があるので、より好ましくは５０℃〜２５０℃の範囲とする。反応温度を一定にするために、上記反応器に公知の冷却装置、加熱装置を設置してもよい。また、反応圧力は、原料化合物の種類や反応温度によって異なるが、減圧、常圧、加圧のいずれであってもよく、通常２０〜１×１０６Ｐａの範囲とする。 The reaction temperature is in the range of 20 ° C to 300 ° C. In order to increase the reaction rate, a high temperature is preferable, but on the other hand, an unfavorable reaction may occur at a high temperature. Therefore, the temperature is more preferably in the range of 50 ° C to 250 ° C. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor. Moreover, although reaction pressure changes with the kind of raw material compound and reaction temperature, any of pressure reduction, a normal pressure, and pressurization may be sufficient, and it is set as the range of 20-1x10 < 6 > Pa normally.
反応時間（連続法の場合は滞留時間）は、特に制限はなく通常０．００１〜５０時間、好ましくは０．０１〜１０時間、より好ましくは０．１〜５時間である。また、反応液を採取し、例えば、液体クロマトグラフィーによって目的化合物が所望量生成していることを確認して反応を終了することもできる。 The reaction time (in the case of a continuous method) is not particularly limited, and is usually 0.001 to 50 hours, preferably 0.01 to 10 hours, more preferably 0.1 to 5 hours. In addition, the reaction solution can be collected and the reaction can be terminated after confirming that the desired compound is produced in a desired amount by, for example, liquid chromatography.
以上に示した方法によって得られるウレイド基を有する化合物は、下記一般式（２）で表される化合物である。式中、Ｒ１は、炭素数１〜２０のｎ価の脂肪族基又は炭素数６〜２０のｎ価の芳香族基を示し、ｎは、２〜１０の整数を示す。なお、Ｒ１は上記イソシアネートに由来するものである。
このような化合物としては、例えば、ヘキサメチレンビスウレア、トリレンビスウレア（各異性体）、ジフェニルメタンビスウレア（各異性体）、イソホロンビスウレア、ジシクロヘキシルメタンビスウレア（各異性体）、ナフタレンビスウレア（各異性体）、テトラメチレンキシリレンビスウレア（各異性体）、トリメチルヘキサメチレンビスウレア（各異性体）、キシリレンビスウレア（各異性体）、水添キシリレンビスウレア（各異性体）、ノルボルネンビスウレア等を挙げることができる。 Examples of such compounds include hexamethylene bis urea, tolylene bis urea (each isomer), diphenylmethane bis urea (each isomer), isophorone bis urea, dicyclohexyl methane bis urea (each isomer), and naphthalene bis urea. (Each isomer), tetramethylene xylylene bis urea (each isomer), trimethylhexamethylene bis urea (each isomer), xylylene bis urea (each isomer), hydrogenated xylylene bis urea (each isomer) And norbornene bisurea.
以上に示した方法は、ウレイド基を有する化合物を簡便に収率よく製造できるため、本発明は、産業上極めて重要である。 Since the method shown above can easily produce a compound having a ureido group with a high yield, the present invention is extremely important industrially.
以下、本発明を実施例に基づき具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, the scope of the present invention is not limited to these Examples.
＜分析方法＞
ＮＭＲ分析により行った。
装置：日本国、日本電子（株）社製ＪＮＭ−Ａ４００ ＦＴ−ＮＭＲシステム
<Analysis method>
Performed by NMR analysis.
Apparatus: JNM-A400 FT-NMR system manufactured by JEOL Ltd., Japan
（１）１Ｈ、１３Ｃ及び１１９Ｓｎ−ＮＭＲ分析サンプルの調製
サンプルを約０．３ｇ秤量し、重クロロホルム（米国、アルドリッチ社製、９９．８％）を約０．７ｇ、及び内部標準物質としてテトラメチルスズ（日本国、和光純薬工業社製、和光一級）を０．０５ｇ加えて均一に混合した溶液をＮＭＲ分析サンプルとした。
(1) Preparation of 1 H, 13 C, and 119 Sn-NMR analysis sample About 0.3 g of a sample was weighed, about 0.7 g of deuterated chloroform (US, Aldrich, 99.8%), and an internal standard substance As a NMR analysis sample, 0.05 g of tetramethyltin (manufactured by Wako Pure Chemical Industries, Japan, Wako First Grade) was added and mixed uniformly.
［実施例１］
内容積２Ｌの４つ口フラスコに、ヘキサメチレンジイソシアネート（日本国、東京化成社製、特級）２０ｇ（１２０ｍｍｏｌ）と、水分量測定の結果、含水量が１５ｐｐｍであったアセトニトリル（日本国、和光純薬工業社製、脱水）１０００ｇ（２４ｍｏｌ）を入れ、ジムロート冷却器及び温度計を取り付け、該フラスコ内を真空−窒素置換した。該フラスコを、１０℃に保持した水浴に浸漬し、アンモニアガス（住友精化社製、半導体ガス、含水量０．３ｐｐｍ）を約２０ｃｃ／分で吹き込み、約６０分間反応をおこなった。該フラスコ内に白色沈殿が生成し、該白色沈殿を濾紙（東洋濾紙社製、５Ｃ）で濾過した。濾別された該白色沈殿は２０．８ｇであった。該白色沈殿についてＮＭＲ測定を行ったところ、該白色沈殿は１，６−ヘキサンジウレアであった。ヘキサメチレンジイソシアネートに対する１，６−ヘキサンジウレアの収率は８６％であった。
[Example 1]
In a four-necked flask with an internal volume of 2 L, 20 g (120 mmol) of hexamethylene diisocyanate (Japan, manufactured by Tokyo Chemical Industry Co., Ltd.) and acetonitrile with a water content of 15 ppm as a result of water content measurement (Japan, Jun Wako Pure) Yakugyo Co., Ltd., dehydration) 1000 g (24 mol) was added, a Dimroth condenser and a thermometer were attached, and the inside of the flask was replaced with vacuum-nitrogen. The flask was immersed in a water bath maintained at 10 ° C., and ammonia gas (manufactured by Sumitomo Seika Co., Ltd., semiconductor gas, water content: 0.3 ppm) was blown at about 20 cc / min, and the reaction was performed for about 60 minutes. A white precipitate was formed in the flask, and the white precipitate was filtered with a filter paper (5C, manufactured by Toyo Roshi Kaisha, Ltd.). The white precipitate separated by filtration was 20.8 g. When NMR measurement was performed on the white precipitate, the white precipitate was 1,6-hexanediurea. The yield of 1,6-hexanediurea based on hexamethylene diisocyanate was 86%.
［比較例１］
ヘキサメチレンジイソシアネートを２１ｇ（１２５ｍｍｏｌ）を使用し、水分量測定の結果、含水量が１１０ｐｐｍであったアセトニトリル１０００ｇ（２４ｍｏｌ）を使用した以外は、実施例１と同様の方法を実施した。生成した白色沈殿を濾紙で濾過したところ、濾別された該白色沈殿は８．８ｇであった。該白色沈殿についてＮＭＲ測定をおこなったところ、該白色沈殿は１，６−ヘキサンジウレアであった。ヘキサメチレンジイソシアネートに対する１，６−ヘキサンジウレアの収率は３５％であった。
[Comparative Example 1]
The same method as in Example 1 was carried out except that 21 g (125 mmol) of hexamethylene diisocyanate was used and 1000 g (24 mol) of acetonitrile having a water content of 110 ppm was used as a result of measuring the water content. The produced white precipitate was filtered with a filter paper, and the white precipitate separated by filtration was 8.8 g. When NMR measurement was performed on the white precipitate, the white precipitate was 1,6-hexanediurea. The yield of 1,6-hexanediurea based on hexamethylene diisocyanate was 35%.
本発明のウレイド基を有する化合物の製造方法は、ウレイド基を有する化合物を簡便に収率よく製造できるため、産業上極めて重要である。 The method for producing a compound having a ureido group according to the present invention is extremely important industrially because a compound having a ureido group can be easily produced in a high yield.
Claims (6)
前記反応が溶媒中で行われ、
前記溶媒に含有される水の量が０．０１ｐｐｍ〜２０ｐｐｍ、前記アンモニアに含有される水の量が０．００１ｐｐｍ〜１０ｐｐｍである製造方法。 A method for producing a compound having a ureido group by a reaction between an isocyanate and ammonia,
The reaction is carried out in a solvent;
The production method wherein the amount of water contained in the solvent is 0.01 ppm to 20 ppm, and the amount of water contained in the ammonia is 0.001 ppm to 10 ppm.
［式中、Ｒ１は、炭素数１〜２０のｎ価の脂肪族基又は炭素数６〜２０のｎ価の芳香族基を示し、ｎは、２〜１０の整数を示す。］ The manufacturing method according to claim 1, wherein the isocyanate is a compound represented by the following general formula (1).
[Wherein, R 1 represents an n-valent aliphatic group having 1 to 20 carbon atoms or an n-valent aromatic group having 6 to 20 carbon atoms, and n represents an integer of 2 to 10]. ]
［式中、Ｒ１は、炭素数１〜２０のｎ価の脂肪族基又は炭素数６〜２０のｎ価の芳香族基を示し、ｎは、２〜１０の整数を示す。］ The method according to claim 1 or 2, wherein the compound having a ureido group is a compound represented by the following general formula (2).
[Wherein, R 1 represents an n-valent aliphatic group having 1 to 20 carbon atoms or an n-valent aromatic group having 6 to 20 carbon atoms, and n represents an integer of 2 to 10]. ]
The said solvent is an aromatic hydroxy compound, The manufacturing method as described in any one of Claims 1-4.
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