Chloro(3,6,13,16-tetraethyl-2,7,12,17-tetramethylporphycenato-kappa4N)iron(III) chloroform solvate.

The X-ray crystallographic analysis of the title complex, chloro[3,10,13,20-tetraethyl-4,9,14,19-tetramethylpentacyclo[16.2.1.1(2,5).1(8,11).1(12,15)]tetracosa-2,4,6,8(23),9,12,14,16,18(21),19-decaene]iron(III) chloroform solvate, [Fe(C(33)H(37)N(4))Cl].CHCl(3), reveals a twisted macrocyclic framework with a slightly distorted rectangular pyramidal core, where the deviation of the central Fe(III) atom from the least-squares plane of the C(20)N(4) core is 0.594 (1) A. Some important bond distances are as follows: Fe-N 2.019 (3), 2.026 (3), 2.028 (3) and 2.034 (3) A; Fe-Cl 2.232 (1) A.

Factors affecting the electronic ground state of low-spin iron(III) porphyrin complexes.

To determine the factors affecting the ground-state electron configuration of low-spin Fe(III) porphyrin complexes, we have examined the (1)H NMR, (13)C NMR, and EPR spectra of a series of low-spin bis-ligated Fe(III) porphyrin complexes [Fe(Por)L(2)](+/-), in which the positions of porphyrin substituents and the coordination ability of axial ligands are different. The seven porphyrins used in this study are meso-tetraalkylporphyrins (TRP: R is propyl, cyclopropyl, or isopropyl), meso-tetraphenylporphyrin (TPP), meso-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin, and 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18-octaalkylporphyrins (ORTPP: R is methyl or ethyl). The porphyrin cores of TRP are more or less S(4)-ruffled depending on the bulkiness of the alkyl substituents, while those of ORTPP are highly S(4)-saddled. Three types of axial ligands are examined which have the following characteristics in ligand field theory: they are (i) strong sigma-donating imidazole (HIm), (ii) strong sigma-donating and weak pi-accepting cyanide (CN(-)), and (iii) weak sigma-donating and strong pi-accepting tert-butyl isocyanide ((t)BuNC). In the case of the bis(HIm) complexes, only the isopropyl complex, [Fe(T(i)PrP)(HIm)(2)](+), has shown the less common (d(xz), d(yz))(4)(d(xy))(1) ground state; the other six complexes have exhibited the common (d(xy))(2)(d(xz), d(yz))(3) ground state. When the axial imidazole is replaced by cyanide, even the propyl and cyclopropyl complexes have shown the (d(xz), d(yz))(4)(d(xy))(1) ground state; the TPP and ORTPP complexes have still maintained the common (d(xy))(2)(d(xz), d(yz))(3) ground state. In the case of the bis((t)()BuNC) complexes, all the complexes have shown the (d(xz), d(yz))(4)(d(xy))(1) ground state. However, the contribution of the (d(xz), d(yz))(4)(d(xy))(1) state to the electronic ground state differs from complex to complex; the (d(xz), d(yz))(4)(d(xy))(1) contribution is the largest in [Fe(T(i)PrP)((t)()BuNC)(2)](+) and the smallest in [Fe(OETPPP)((t)BuNC)(2)](+). We have then examined the electronic ground state of low-spin [Fe(OEP)((t)BuNC)(2)](+) and [Fe(ProtoIXMe(2))((t)BuNC)(2)](+); OEP and ProtoIXMe(2) represent 2,3,7,8,12,13,17,18-octaethylporphyrin and protoporphyrin-IX dimethyl ester, respectively. These porphyrins have a(1u) HOMO in contrast to the other seven porphyrins that have a(2u) HOMO. The (13)C NMR and EPR studies have revealed that the contribution of the (d(xz), d(yz))(4)(d(xy))(1) state in these complexes is as small as that in [Fe(OETPP)((t)BuNC)(2)](+). On the basis of these results, we have concluded that the low-spin iron(III) porphyrins that have (i) strong axial ligands, (ii) highly saddle shaped porphyrin rings, (iii) porphyrins with a(1u) HOMO, and (iv) electron withdrawing substituents at the meso positions tend to maintain the common (d(xy))(2)(d(xz), d(yz))(3) ground state.

(12,17-diethoxycarbonyl-2,3,6,7,11,18-hexamethylcorrphycenato-kappa4N)iodoiron(III) chloroform solvate.

The title complex, (diethyl 3,4,8,15,19,20-hexamethyl-21,22,23,24-tetraazopentacyclo[16.2.1.1(2,5).1(7,11).1(14,17)]tetracosa-1(20),2(22),3,5,7,9,11,13(24),14,16,18-undecaene-9,14-dicarboxylate-kappa4N)iodoiron(III) chloroform solvate, [Fe(C32H32N4O4)I].CHCl3, shows an almost planar arrangement of the corrphycene moiety with a slightly distorted trapezoid pyramidal core; the Fe(III) atom is 0.416 (1) A from the plane of the C20N4 system. The Fe-N distances are 2.049 (3), 2.044 (3), 2.079 (3) and 2.075 (3) A. The solvated chloroform forms a C-H...O hydrogen bond [C...O 3.107 (10) A] to an adjacent carbonyl O atom. This is the first X-ray structure analysis of a corrphycenatoiron(III) derivative.

Bis(tetrahydrofuran-kappa O)(meso-5,10,15,20-tetraisopropylporphyrinato-kappa(4)N)iron(III) perchlorate.

The title complex, [Fe(C(32)H(36)N(4))(C(4)H(8)O)(2)]ClO(4), shows an S(4)-ruffled porphyrin ring, where the maximum deviation of the meso-carbon from the least-squares plane of the [Fe(C(20)N(4))] core is as high as 0.675 (9) A. This is the highest class of deviation among S(4)-ruffled iron(III) porphyrin complexes. The average Fe-N(p) bond distance is 1.967 (12) A (N(p) denotes an N atom of the equatorial ligand).

(2-Carbamoylethyl)bis(dimethylglyoximato-N, N')

The 2-carbamoylethyl and 2-(methylcarbamoyl)ethyl groups in the title cobaloxime complexes, [Co(C(4)H(7)N(2)O(2))(2)(C(3)H(6)NO)(C(12)H(13)N)].C(2)H(6)O and [Co(C(4)H(7)N(2)O(2))(2)(C(4)H(8)NO)(C(10)H(13)NO(2))], were isomerized to 1-carbamoylethyl and 1-(methylcarbamoyl)ethyl groups, respectively, on exposure to visible light in the solid state. Although both the crystal structures and the intermolecular hydrogen bonds are different in the two crystals, similar reaction rates were observed.

[Comparisons of histological grading between biopsy and radical prostatectomy specimens in prostatic adenocarcinoma].

PURPOSE: To examine how accurately biopsy specimens reflect the corresponding excised specimens in terms of histologic grades of prostatic adenocarcinoma, histologic grades of biopsy specimens were compared to those of radical prostatectomy specimen in 29 patients who underwent radical prostatectomy without any prior treatment. METHODS: For the assessment of histological grading, Japanese General Rule for Prostatic Cancer (JGRPC), in which adenocarcinoma was graded as being either well, moderately or poorly differentiated, and Gleason's system were applied. RESULTS: According to JGRPC, histologic grades of biopsy specimens were identical to those of the prostatectomy specimens in 83% of cases, with biopsy specimens given higher grades than those of the prostatectomy specimen in 4 (14%), and lower grades in 1 (3%). According to Gleason score histological grade of biopsy specimens were identical to those of the prostatectomy specimens in only 52%. However, the grouping category of Gleason score (2 to 5, 6, 7 and 8 to 10) assigned to the biopsy was lower than that of prostatectomy specimen in only 3 cases (10%) and was greater than that of prostatectomy specimen in 5 cases (17%). CONCLUSION: These results suggest that histological grades based upon biopsy specimens will predict those of the corresponding prostatectomy specimens in the majority (72% to 83%) but not all of the cases.

[A case of primary signet ring cell carcinoma of urinary bladder].

A 72-year-old female patient presented to our clinic with the chief complaint of gross hematuria and urinary frequency on September 6, 1990. Cystoscopic examination revealed a thumb's head size nonpapillary tumor. The tumor was located adjacent to the orifice of the left ureter. Histological findings of the tumor by transurethral resection (TUR) indicated transitional cell carcinoma with partial signet ring cell carcinoma. No other malignant findings in any other organs including the gastrointestinal tract were noted. Total cystectomy was performed and Indiana pouch was constructed. Histopathological staging was pT1 N0 M0. The patient died of multiple metastasis of the signet ring cell carcinoma on June 22, 1992. This is the thirty-second case of signet ring cell carcinoma of urinary bladder reported in the medical literature in Japan. We investigated 19 alive or unknown cases as follow up and briefly discussed the treatment and outcome of the primary signet ring cell carcinoma of the urinary bladder. The outcome appeared to be somewhat better than previous reports. Total cystectomies were performed in 18 of the 32 cases (56.3%). As noted in past reports, the treatment of our patient consisted of total cystectomy. Twenty-two patients died of signet ring cell carcinoma. Recurrence to the pelvic area was observed in 18 of the 22 (81.8%) patients who died. Because of this high rate of recurrence, we recommend a thorough assessment of the pelvic area of the patients diagnosed with signet ring cell carcinoma of urinary bladder.

[Clinical study of 22 cases of torsion of the spermatic cord].

We performed surgical treatment in 22 cases of torsion of the spermatic cord during the past sixteen years. Orchiopexy was performed in 9 cases, but in 13 cases orchiectomy was unavoidable. For five patients the visit to a doctor was too late. In five other cases a mistaken diagnosis was made by local medical doctors. Improvement of the success rate of orchiopexy requires that adolescents, their families and teachers should learn to recognize this disease, and doctors of other departments should recognize it as acute scrotum.

Design and synthesis of regioselective cleaving reagents for oligonucleotides.

Reaction of methyl 2,3-anhydro-alpha-D-ribofuranoside with allylmagnesium chloride selectively took place at the 2-C position to afford methyl 2-C-allyl-2-deoxy-alpha-D-arabinofuranoside. 1-O-Acetyl-2,3,5-tri-O-benzoyl-beta-D-ribofuranose reacted with allylic alcohols in the presence of BF3.OEt2 to give the corresponding allyl beta-D-ribofuranosides. The allyl group in these compounds were converted into a variety of functional groups which include bromoacetoxy, oxylanyl, tosyloxy, and azide.